CN103153861B - Ammonia purification system and method for purifying ammonia - Google Patents
Ammonia purification system and method for purifying ammonia Download PDFInfo
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- CN103153861B CN103153861B CN201180048862.6A CN201180048862A CN103153861B CN 103153861 B CN103153861 B CN 103153861B CN 201180048862 A CN201180048862 A CN 201180048862A CN 103153861 B CN103153861 B CN 103153861B
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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
- C01C1/024—Purification
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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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
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Abstract
The present invention provides an ammonia purification system capable of purifying ammonia in a simplified method and of effectively purifying ammonia by reducing energy consumption. The ammonia purification system (100) includes an oil adsorption tower (2), a high boiling impurities adsorption unit (3) and a vaporizer (5). The oil adsorption tower (2) adsorbs and removes oil contained in liquid crude ammonia by activated carbon. The high boiling impurities adsorption unit (3) adsorbs and removes high boiling impurities contained in the liquid ammonia by synthetic zeolite. The vaporizer (5) vaporizes the liquid ammonia delivered from the high boiling impurities adsorption unit (3) at a predetermined vaporization rate, and separates and removes low boiling impurities as a gaseous phase component.
Description
Technical field
The present invention relates to and the Ammonia purification system of (purification) and the process for purification of ammonia are refined to thick ammonia.
Background technology
In semiconductor fabrication sequence and liquid crystal manufacturing process, utilize highly purified ammonia as the treatment agent of the making for nitride tunicle etc.Highly purified ammonia is like this refining to remove impurity to obtain by carrying out thick ammonia.
The low-boiling point gas such as lower hydrocarbon, the higher hydrocarbon with more carbonatoms, moisture and hydrogen, nitrogen, oxygen, argon gas, carbon monoxide such as methane, ethane, propane are contained as impurity in thick ammonia.The purity of usual obtainable thick ammonia is about 99.5 % by weight.
Different according to the kind of the operation of the use ammonia in semiconductor fabrication sequence and liquid crystal manufacturing process, the influence mode of the impurity in ammonia is different, but as the purity of ammonia, requirement is more than 99.9999 % by weight, is more preferably more than 99.99999 % by weight.
As the method for the impurity contained in the thick ammonia of removing, there will be a known: use the sorbent materials such as silica gel, synthetic zeolite, gac to adsorb the method for removing impurity; The method of distillation removing impurity.
Such as, Patent Document 1 discloses a kind of Ammonia purification system, it possesses: from liquid thick ammonia, remove the 1st distillation tower of high-boiling-point impurity, the adsorption tower removed by adsorbent by the impurity (being mainly moisture) that contains in the gasiform ammonia of deriving from the 1st distillation tower and by the 2nd distillation tower removing lower-boiling impurity in the gasiform ammonia of deriving from adsorption tower.In addition, Patent Document 2 discloses after utilizing the sorbent material be made up of barium oxide the water adsorption contained in gasiform thick ammonia to be removed, distill, thus to the method that ammonia is refined.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-206410 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-183021 publication
Summary of the invention
Invent problem to be solved
In the technology of disclosed in patent documentation 1,2, ammonia being refined, the impurity contained in thick ammonia is removed by absorption tower adsorbs, further by distillation tower distillation removing, thus ammonia is refined.But from distillation tower derive refining after gasiform ammonia be condensed thus be recovered with the form of ammonia liquor.Namely, in the disclosed technology that ammonia is refined of patent documentation 1,2, the impurity contained in thick ammonia is carried out adsorb, distill removing, carry out condensation again, thus obtain the ammonia liquor of refining, therefore as the method for refining ammonia, not talkative is the method simplified, and carries out a large amount of energy of refining needs to ammonia.
Therefore, the object of the present invention is to provide and can carry out refining by the method that simplifies to ammonia and the consumption of energy can be suppressed thus the process for purification of the Ammonia purification system of effectively ammonia being refined and ammonia.
For the means of dealing with problems
The present invention is a kind of Ammonia purification system, and it is the Ammonia purification system of refining the thick ammonia containing impurity, it is characterized in that, comprises:
Reservoir, the thick ammonia of its storing liquid shape;
1st adsorption section, the oil content contained in the liquid thick ammonia stored in above-mentioned reservoir is removed by charcoal absorption by it, the ammonia of tapping shape;
2nd adsorption section, high-boiling-point impurity higher than ammonia for the boiling point contained in the liquid ammonia of deriving from above-mentioned 1st adsorption section is removed by synthetic zeolite absorption by it, the ammonia of tapping shape; With
Gasification portion, the liquid ammonia of deriving from above-mentioned 2nd adsorption section carries out gasifying with the vaporization rate of regulation and is separated into gas phase composition and liquid composition by it, thus lower-boiling impurity lower than ammonia for boiling point is removed with the isolated in form of gas phase composition, obtain the ammonia liquor after refining with the form of liquid composition.
In addition, about Ammonia purification system of the present invention, preferably, also comprise the analysis portion analyzed the concentration of the impurity contained in the liquid ammonia of deriving from above-mentioned 2nd adsorption section, above-mentioned gasification portion sets the vaporization rate of afore mentioned rules when being gasified by the liquid ammonia of deriving from above-mentioned 2nd adsorption section based on the analytical results obtained by above-mentioned analysis portion.
In addition, about Ammonia purification system of the present invention, the vaporization rate of afore mentioned rules when gasifying to the liquid ammonia of deriving from above-mentioned 2nd adsorption section is set as 5 ~ 20 volume % by preferred above-mentioned gasification portion.
In addition, about Ammonia purification system of the present invention, the liquid ammonia of deriving from above-mentioned 2nd adsorption section carries out gasifying and is separated into gas phase composition and liquid composition by preferred above-mentioned gasification portion at the temperature of-50 ~ 30 DEG C.
In addition, about Ammonia purification system of the present invention, preferably above-mentioned 2nd adsorption section has: be filled with the 1st adsorption zone as the MS-3A of synthetic zeolite and the 2nd adsorption zone being filled with the MS-13X as synthetic zeolite.
In addition, about Ammonia purification system of the present invention, preferably above-mentioned 2nd adsorption section has multiple adsorption sections connected in series or in parallel, the high-boiling-point impurity absorption removing that the plurality of adsorption section will be contained in the liquid ammonia of deriving from above-mentioned 1st adsorption section.
In addition, the present invention is a kind of process for purification of ammonia, and it is the method for refining the thick ammonia containing impurity, it is characterized in that, comprises:
Storage operation, the wherein thick ammonia of storing liquid shape,
1st absorption process, is wherein removed the oil content contained in the liquid thick ammonia stored in above-mentioned storage operation by charcoal absorption;
2nd absorption process, wherein by high-boiling-point impurity higher than ammonia for the boiling point that contains in the liquid ammonia after absorption eliminates oil content in above-mentioned 1st absorption process by synthetic zeolite absorption removing; With
Gasification process, wherein the liquid ammonia after absorption eliminates high-boiling-point impurity in above-mentioned 2nd absorption process is carried out gasifying with the vaporization rate of regulation and is separated into gas phase composition and liquid composition, thus lower-boiling impurity lower than ammonia for boiling point is removed with the isolated in form of gas phase composition, obtain the ammonia liquor after refining with the form of liquid composition.
Invention effect
According to the present invention, Ammonia purification system is the system of refining the thick ammonia containing impurity, and it comprises reservoir, the 1st adsorption section, the 2nd adsorption section and gasification portion.The oil content contained in the liquid thick ammonia stored in reservoir is removed by charcoal absorption by the 1st adsorption section.The high-boiling-point impurity contained in the liquid ammonia of deriving from the 1st adsorption section is removed by synthetic zeolite absorption by the 2nd adsorption section.In addition, the liquid ammonia of deriving from the 2nd adsorption section carries out gasifying with the vaporization rate of regulation and is separated into gas phase composition and liquid composition by gasification portion, thus lower-boiling impurity is removed with the isolated in form of gas phase composition, obtain the ammonia liquor after refining with the form of liquid composition.
In Ammonia purification system of the present invention, liquid ammonia after absorption is eliminated the high-boiling-point impurities such as oil content, moisture, higher hydrocarbon by gasification portion carries out gasifying with the vaporization rate of regulation and is separated into gas phase composition and liquid composition, therefore the lower-boiling impurities such as low-boiling point gas such as the lower hydrocarbon such as methane, ethane, propane and hydrogen, nitrogen, oxygen, argon gas, carbon monoxide are removed with the isolated in form of gas phase composition, the ammonia liquor after refining can be obtained with the form of liquid composition.Therefore, Ammonia purification system of the present invention can be refined ammonia by the method simplified when not carrying out the distillation along with backflow as conventional art, and can suppress the consumption of energy thus effectively refine ammonia.
In addition, according to the present invention, Ammonia purification system also comprises analysis portion.The concentration of this analysis portion to the impurity contained in the liquid ammonia of deriving from the 2nd adsorption section is analyzed.In addition, gasification portion based on the analytical results obtained by analysis portion set by from the 2nd adsorption section derive liquid ammonia gasify time vaporization rate.Like this, gasification portion sets vaporization rate when being gasified by liquid ammonia according to the analytical results obtained by analysis portion, therefore can suppress the consumption of energy thus effectively refine ammonia.
In addition, according to the present invention, the liquid ammonia of deriving from the 2nd adsorption section carries out gasifying with the vaporization rate of 5 ~ 20 volume % and is separated into gas phase composition and liquid composition by gasification portion.Thus, the lower-boiling impurity contained in the liquid ammonia after absorption is eliminated oil content and high-boiling-point impurity removes with the isolated in form of gas phase composition, effectively can obtain the ammonia liquor after refining with the form of liquid composition.
In addition, according to the present invention, the liquid ammonia of deriving from the 2nd adsorption section carries out gasifying and is separated into gas phase composition and liquid composition by gasification portion at the temperature of-50 ~ 30 DEG C.Thus, the liquid ammonia after absorption is eliminated oil content and high-boiling-point impurity gasifies effectively, thus can obtain being separated the ammonia liquor after eliminating lower-boiling impurity, and can improve the purity of this ammonia liquor.
In addition, according to the present invention, the 2nd adsorption section has: be filled with the 1st adsorption zone as the MS-3A of synthetic zeolite and the 2nd adsorption zone being filled with MS-13X.Synthetic zeolite MS-3A is sorbent material moisture to excellent adsorptive power.MS-13X is sorbent material moisture and hydrocarbon to excellent adsorptive power.By forming the 2nd adsorption section with the adsorption zone being filled with MS-3A and MS-13X with such adsorptive power, the high-boiling-point impurity such as moisture, higher hydrocarbon contained can be adsorbed removing effectively in the liquid ammonia of deriving from the 1st adsorption section.
In addition, according to the present invention, the 2nd adsorption section has multiple adsorption sections connected in series or in parallel.When the 2nd adsorption section has the multiple adsorption section be connected in series, the absorption removing ability for the high-boiling-point impurity contained in the liquid ammonia of deriving from the 1st adsorption section can be improved.In addition, when the 2nd adsorption section has the multiple adsorption section be connected in parallel, the liquid ammonia of deriving from the 1st adsorption section can be imported to the multiple adsorption sections be connected in parallel with the state of separating separately, therefore, it is possible to using other adsorption sections be over to carry out manipulation of regeneration to make to use other adsorption sections be over again can carry out absorption removing action during an adsorption section carries out adsorbing removing.
In addition, according to the present invention, the process for purification of ammonia is the method for refining the thick ammonia containing impurity, and it comprises storage operation, the 1st absorption process, the 2nd absorption process and gasification process.In 1st absorption process, the oil content contained in the liquid thick ammonia stored in storage operation is removed by charcoal absorption.In 2nd absorption process, removed adsorbing the high-boiling-point impurity contained in the liquid ammonia after eliminating oil content in the 1st absorption process by synthetic zeolite absorption.In addition, in gasification process, liquid ammonia after absorption eliminates high-boiling-point impurity in the 2nd absorption process is carried out gasifying with the vaporization rate of regulation and is separated into gas phase composition and liquid composition, thus lower-boiling impurity is removed with the isolated in form of gas phase composition, obtain the ammonia liquor after refining with the form of liquid composition.
In the process for purification of ammonia of the present invention, in gasification process, liquid ammonia after absorption is eliminated oil content and the high-boiling-point impurity such as moisture, higher hydrocarbon carries out gasifying with the vaporization rate of regulation and is separated into gas phase composition and liquid composition, therefore the lower-boiling impurities such as low-boiling point gas such as the lower hydrocarbon such as methane, ethane, propane and hydrogen, nitrogen, oxygen, argon gas, carbon monoxide are removed with the isolated in form of gas phase composition, the ammonia liquor after refining can be obtained with the form of liquid composition.Therefore, the process for purification of ammonia of the present invention can be refined ammonia by the method simplified when not carrying out the distillation along with backflow as conventional art, and can suppress the consumption of energy thus effectively refine ammonia.
Accompanying drawing explanation
Fig. 1 is the figure of the formation of the Ammonia purification system 100 representing the 1st embodiment of the present invention.
Fig. 2 is the figure of the formation of the Ammonia purification system 200 representing the 2nd embodiment of the present invention.
Embodiment
Fig. 1 is the figure of the formation of the Ammonia purification system 100 representing the 1st embodiment of the present invention.The Ammonia purification system 100 of present embodiment is the system of refining the liquid thick ammonia containing impurity.The low-boiling point gas such as the lower hydrocarbon such as oil content and methane, ethane, propane, the higher hydrocarbon with more carbonatomss, moisture and hydrogen, nitrogen, oxygen, argon gas, carbon monoxide are contained as impurity in liquid thick ammonia.That is, containing oil content, the boiling point lower-boiling impurity such as lower hydrocarbon, low-boiling point gas lower than ammonia (boiling point is-33.44 DEG C) and the boiling point high-boiling-point impurity such as higher hydrocarbon, moisture higher than ammonia in liquid thick ammonia.
Comprise in the formation of Ammonia purification system 100 hold tank 1 as reservoir, the oil adsorption tower 2 as the 1st adsorption section, high-boiling-point impurity adsorption section 3 as the 2nd adsorption section, analysis portion 4, as the gasifier 5 in gasification portion and withdrawing can 6.In addition, Ammonia purification system 100 realizes the process for purification of ammonia of the present invention, implements storage operation, in oil adsorption tower 2, implement the 1st absorption process in hold tank 1, in high-boiling-point impurity adsorption section 3, implement the 2nd absorption process, in gasifier 5, implement gasification process.
Hold tank 1 is the tank storing thick ammonia.In present embodiment, in hold tank 1, the purity of the thick ammonia of storage is about 99.5 % by weight.
As long as hold tank 1 has the insulating container of resistance to pressure and erosion resistance just, have no particular limits.This hold tank 1 stores thick ammonia with the form of liquid ammonia, and is controlled to make temperature and pressure reach controlled condition.Under the state that hold tank 1 stores liquid thick ammonia, form gas phase on the top of hold tank 1, form liquid phase in bottom.In present embodiment, when thick ammonia is exported in oil adsorption tower 2 from hold tank 1, thick ammonia is derived with the form of liquid thick ammonia from above-mentioned liquid phase.Between hold tank 1 with oil adsorption tower 2, be connected the 1st pipe arrangement 81, flow through the 1st pipe arrangement 81 from the liquid thick ammonia of hold tank 1 derivation and be supplied to oil adsorption tower 2.
The 1st valve 811 of the stream opened or closed in the 1st pipe arrangement 81 is provided with in the 1st pipe arrangement 81.When liquid thick ammonia supplies in oil adsorption tower 2, the 1st valve 811 is opened, and liquid thick ammonia flows through in the 1st pipe arrangement 81 from hold tank 1 towards oil adsorption tower 2.
Lubrication wet goods oil content about 2 ~ 15ppm containing equipment such as compressors in the liquid thick ammonia of deriving from hold tank 1.After can making thick ammonia by oil content meter (OCMA-355, Horiba Ltd's system) mensuration, residual one-tenth assigns to obtain the content of the oil content contained in this liquid thick ammonia.
The oil content absorption removing that oil adsorption tower 2 will be contained in the liquid thick ammonia of deriving from hold tank 1 by the sorbent material be made up of gac.As the gac be filled in oil adsorption tower 2, can list: activated coco nut charcoal (KURARAY GG, KURARAY CHEMICAL Co., Ltd. system) etc.
The liquid ammonia of deriving from oil adsorption tower 2 flows through the 2nd pipe arrangement 82, thus is supplied in the 3rd pipe arrangement 83 be connected with high-boiling-point impurity adsorption section 3.
2nd pipe arrangement 82 is provided with the strainer 7 for removing the heavy metal contained the liquid ammonia that flows through from oil adsorption tower 2 towards the 3rd pipe arrangement 83.In present embodiment, strainer 7 has 2 Rotating fields that 5 μm of strainers that polypropylene (PP) makes are connected with 0.01 μm of positioned inline of tetrafluoroethylene (PTFE)/PP.It should be noted that, strainer 7 is not limited to more configure with being directly connected by the downstream side, direction of flowing through of ammonia with than oil adsorption tower 2, also can configure in the downstream side, direction of flowing through of the ammonia of high-boiling-point impurity adsorption section 3 described later.In addition, in Fig. 1, show the formation that 1 strainer 7 is set on the 2nd pipe arrangement 82, but be not limited to this formation, also multiple strainer 7 and the 2nd pipe arrangement 82 can be connected in parallel.Such as, when forming the formation 2 strainers 7 and the 2nd pipe arrangement 82 are connected in parallel, during the heavy metal contained in the liquid ammonia of deriving from oil adsorption tower 2 is carried out filtering separation removing by a strainer 7, the exchanging operation using other strainers 7 be over can be carried out.
In addition, on the 2nd pipe arrangement 82, than strainer 7 more by ammonia flow through the 2nd valve 821 that direction upstream side is provided with the stream opened or closed in the 2nd pipe arrangement 82.When liquid ammonia supplies from oil adsorption tower 2 towards the 3rd pipe arrangement 83, the 2nd valve 821 is opened, and liquid ammonia is flow through in the 2nd pipe arrangement 82 by strainer 7.
Flow through the liquid ammonia be supplied in the 3rd pipe arrangement 83 in the 2nd pipe arrangement 82 to be directed in high-boiling-point impurity adsorption section 3.High-boiling-point impurity adsorption section 3 will be derived from oil adsorption tower 2 and by the high-boiling-point impurity adsorbent removing by synthetic zeolite be made up of higher than ammonia of the boiling point that contains in the liquid ammonia of strainer 7.In present embodiment, comprise in the formation of high-boiling-point impurity adsorption section 3 as the 1st adsorption tower 31 of multiple adsorption section, the 2nd adsorption tower 32, the 3rd adsorption tower 33 and the 4th adsorption tower 34.
1st adsorption tower 31 and the 3rd adsorption tower 33 and the 3rd pipe arrangement 83 are connected in parallel.The 3rd valve 831 and the 4th valve 832 of the stream opened or closed in the 3rd pipe arrangement 83 is provided with in the 3rd pipe arrangement 83.In the 3rd pipe arrangement 83, the 3rd valve 831 is configured in the upstream side (that is, the top of tower side of the 1st adsorption tower 31) of the 1st adsorption tower 31, and the 4th valve 832 is configured in the upstream side (that is, the top of tower side of the 3rd adsorption tower 33) of the 3rd adsorption tower 33.When deriving from oil adsorption tower 2 and supplied in the 1st adsorption tower 31 by the liquid ammonia of strainer 7, the 3rd valve 831 is opened, and the 4th valve 832 is closed, and liquid ammonia flows through in the 3rd pipe arrangement 83 from strainer 7 towards the 1st adsorption tower 31.In addition, when deriving from oil adsorption tower 2 and supplied in the 3rd adsorption tower 33 by the liquid ammonia of strainer 7, the 4th valve 832 is opened, and the 3rd valve 831 is closed, and liquid ammonia flows through in the 3rd pipe arrangement 83 from strainer 7 towards the 3rd adsorption tower 33.
Like this, high-boiling-point impurity adsorption section 3 has the 1st adsorption tower 31 and the 3rd adsorption tower 33 that are connected in parallel, can deriving from oil adsorption tower 2 thus and be imported to the state of separating respectively by the liquid ammonia of strainer 7 in the 1st adsorption tower 31 and the 3rd adsorption tower 33 be connected in parallel, therefore such as can carry out adsorbing removing in the 1st adsorption tower 31 during, removing action to using the 3rd adsorption tower 33 be over to carry out manipulation of regeneration to make using the 3rd adsorption tower 33 be over again can carry out absorption.
2nd adsorption tower 32 is connected in series by the 4th pipe arrangement 84 and the 1st adsorption tower 31.That is, the tower bottom in an end of the 4th pipe arrangement 84 with the 1st adsorption tower 31 is connected, and the other end is connected with the top of tower of the 2nd adsorption tower 32.Thus, derive from oil adsorption tower 2 and flow through the 4th pipe arrangement 84 by strainer 7, the liquid ammonia imported to the 1st adsorption tower 31 and be directed in the 2nd adsorption tower 32.Like this, high-boiling-point impurity adsorption section 3 is by having the 1st adsorption tower 31 and the 2nd adsorption tower 32 that are connected in series, can will derive from oil adsorption tower 2 and in the 1st adsorption tower 31 and the 2nd adsorption tower 32, adsorb removing by the high-boiling-point impurity contained in the liquid ammonia of strainer 7, therefore can improve the absorption removing ability for high-boiling-point impurity.
The liquid ammonia of deriving from the 2nd adsorption tower 32 flows through the 5th pipe arrangement 85, is supplied in the 10th pipe arrangement 90 be connected with gasifier 5.
The 5th valve 851 and the 6th valve 852 of the stream opened or closed in the 5th pipe arrangement 85 is provided with in the 5th pipe arrangement 85.In the 5th pipe arrangement 85, what the 5th valve 851 was configured in ammonia flows through direction upstream side (that is, the 2nd adsorption tower 32 side), and what the 6th valve 852 was configured in ammonia flows through downstream side, direction (that is, the 10th pipe arrangement 90 side).When the liquid ammonia of deriving from the 2nd adsorption tower 32 supplies to the 10th pipe arrangement 90, the 5th valve 851 and the 6th valve 852 are opened, and liquid ammonia flows through in the 5th pipe arrangement 85 from the 2nd adsorption tower 32 towards the 10th pipe arrangement 90.
In addition, in the Ammonia purification system 100 of present embodiment, the 8th pipe arrangement 88 being provided with between the 5th valve 851 with the 6th valve 852 from the 5th pipe arrangement 85 branch out, being connected with analysis portion 4.The 9th valve 881 of the stream opened or closed in the 8th pipe arrangement 88 is provided with in the 8th pipe arrangement 88.When deriving from oil adsorption tower 2 and be directed in the 1st adsorption tower 31 and the 2nd adsorption tower 32 by the liquid ammonia of strainer 7, the 9th valve 881 is often opened, and the ammonia of the minute quantity needed for analysis flows through in the 8th pipe arrangement 88 towards analysis portion 4.
4th adsorption tower 34 is connected in series by the 6th pipe arrangement 86 and the 3rd adsorption tower 33.That is, an end of the 6th pipe arrangement 86 is connected with the tower bottom of the 3rd adsorption tower 33, and the other end is connected with the top of tower of the 4th adsorption tower 34.Thus, from oil adsorption tower 2 derive and by strainer 7, import to the liquid ammonia after the 3rd adsorption tower 33 and flow through the 6th pipe arrangement 86 and be directed in the 4th adsorption tower 34.Like this, high-boiling-point impurity adsorption section 3 is by having the 3rd adsorption tower 33 and the 4th adsorption tower 34 that are connected in series, can will derive from oil adsorption tower 2 and in the 3rd adsorption tower 33 and the 4th adsorption tower 34, adsorb removing by the high-boiling-point impurity contained in the liquid ammonia of strainer 7, therefore can improve the absorption removing ability for high-boiling-point impurity.
The liquid ammonia of deriving from the 4th adsorption tower 34 flows through the 7th pipe arrangement 87, is supplied in the 10th pipe arrangement 90 be connected with gasifier 5.
The 7th valve 871 and the 8th valve 872 of the stream opened or closed in the 7th pipe arrangement 87 is provided with in the 7th pipe arrangement 87.In 7th pipe arrangement 87, what the 7th valve 871 was configured in ammonia flows through direction upstream side (that is, the 4th adsorption tower 34 side), and what the 8th valve 872 was configured in ammonia flows through downstream side, direction (that is, the 10th pipe arrangement 90 side).When the liquid ammonia of deriving from the 4th adsorption tower 34 supplies to the 10th pipe arrangement 90, the 7th valve 871 and the 8th valve 872 are opened, and liquid ammonia flows through in the 7th pipe arrangement 87 from the 4th adsorption tower 34 towards the 10th pipe arrangement 90.
In addition, in the Ammonia purification system 100 of present embodiment, the 9th pipe arrangement 89 being provided with between the 7th valve 871 with the 8th valve 872 from the 7th pipe arrangement 87 branch out, being connected with analysis portion 4.The 10th valve 891 of the stream opened or closed in the 9th pipe arrangement 89 is provided with in the 9th pipe arrangement 89.When deriving from oil adsorption tower 2 and be directed in the 3rd adsorption tower 33 and the 4th adsorption tower 34 by the liquid ammonia of strainer 7, the 10th valve 891 is often opened, and the ammonia of the minute quantity needed for analysis flows through in the 9th pipe arrangement 89 towards analysis portion 4.
In addition, in present embodiment, the 1st adsorption tower 31 has: the MS-3A(micropore diameter be filled with as synthetic zeolite is 3
porous synthetic zeolite) the 1st adsorption zone 311 and the MS-13X(micropore diameter be filled with as synthetic zeolite be 9
porous synthetic zeolite) the 2nd adsorption zone 312.In the 1st adsorption tower 31, the 1st adsorption zone 311 and the 2nd adsorption zone 312 are connected in series, at top of tower side configuration the 1st adsorption zone 311, at tower bottom side configuration the 2nd adsorption zone 312.
It should be noted that, the 2nd adsorption tower 32, the 3rd adsorption tower 33 and the 4th adsorption tower 34 are formed respectively in the same manner as the 1st adsorption tower 31.Specifically, in the 2nd adsorption tower 32, be filled with the 1st adsorption zone 321 of MS-3A in the configuration of top of tower side, be filled with the 2nd adsorption zone 322 of MS-13X in the configuration of tower bottom side.In the 3rd adsorption tower 33, be filled with the 1st adsorption zone 331 of MS-3A in the configuration of top of tower side, be filled with the 2nd adsorption zone 332 of MS-13X in the configuration of tower bottom side.In the 4th adsorption tower 34, be filled with the 1st adsorption zone 341 of MS-3A in the configuration of top of tower side, be filled with the 2nd adsorption zone 342 of MS-13X in the configuration of tower bottom side.
Synthetic zeolite MS-3A is sorbent material moisture to excellent adsorptive power, and MS-13X is sorbent material moisture and hydrocarbon to excellent adsorptive power.By forming the 1st adsorption tower 31, the 2nd adsorption tower 32, the 3rd adsorption tower 33 and the 4th adsorption tower 34 with the 1st adsorption zone being filled with the MS-3A with such adsorptive power and the 2nd adsorption zone being filled with MS-13X, can will derive from oil adsorption tower 2 and effectively adsorb removing by the high-boiling-point impurity such as moisture, higher hydrocarbon contained in the liquid ammonia of strainer 7.
The sorbent material be made up of synthetic zeolites such as MS-3A and MS-13X used in present embodiment can make adsorbed impurity (moisture and hydrocarbon) depart from by any one process in heating, decompression, heating and decompression and regenerate.Such as, when being made by heat treated to be departed from by adsorbent impurity, carry out heating at the temperature of 200 ~ 350 DEG C.
In the Ammonia purification system 100 of present embodiment, the temperature of the 1st adsorption tower 31, the 2nd adsorption tower 32, the 3rd adsorption tower 33 and the 4th adsorption tower 34 is controlled as 0 ~ 60 DEG C, and pressure is controlled as 0.1 ~ 1.0MPa.When the temperature of the 1st adsorption tower 31, the 2nd adsorption tower 32, the 3rd adsorption tower 33 and the 4th adsorption tower 34 is lower than 0 DEG C, need the cooling carrying out the heat of adsorption produced when adsorbing removing impurity to be removed, thus energy efficiency likely reduces.When the temperature of the 1st adsorption tower 31, the 2nd adsorption tower 32, the 3rd adsorption tower 33 and the 4th adsorption tower 34 is more than 60 DEG C, the adsorptive power of sorbent material to impurity likely reduces.In addition, when the pressure of the 1st adsorption tower 31, the 2nd adsorption tower 32, the 3rd adsorption tower 33 and the 4th adsorption tower 34 is lower than 0.1MPa, the adsorptive power of sorbent material to impurity likely reduces.When the pressure of the 1st adsorption tower 31, the 2nd adsorption tower 32, the 3rd adsorption tower 33 and the 4th adsorption tower 34 is more than 1.0MPa, in order to maintain under a constant, need a large amount of energy, energy efficiency likely reduces.
In addition, the linear velocity in the 1st adsorption tower 31, the 2nd adsorption tower 32, the 3rd adsorption tower 33 and the 4th adsorption tower 34 is: amount ammonia liquid in time per unit being supplied to each adsorption tower 31,32,33,34 is converted into NTP(normal temperature and pressure) under gas volume and the value obtained divided by the void tower sectional area of each adsorption tower 31,32,33,34 range preferably from 0.01 ~ 0.5m/ second.When on-line velocity is lower than 0.01m/ second, absorption removing impurity needs long-time, therefore not preferred; When on-line velocity is more than 0.5m/ second, the heat of adsorption produced during absorption removing impurity is not fully removed, and the adsorptive power of sorbent material to impurity likely reduces.
Derive from the 2nd adsorption tower 32 and flow through the liquid ammonia of the 8th pipe arrangement 88 or to derive and the liquid ammonia flowing through the 9th pipe arrangement 89 is directed to analysis portion 4 from the 4th adsorption tower 34.
The concentration of analysis portion 4 to the impurity contained in the liquid ammonia of deriving from the 2nd adsorption tower 32 or the 4th adsorption tower 34 is analyzed.In present embodiment, analysis portion 4 is gas chromatographic analysis device (GC-PDD: impulsive discharge type detector).As gas phase analysis device, such as, can list: GC-4000(GL Sciences Co., Ltd. system).In present embodiment, about the liquid ammonia of deriving from the 2nd adsorption tower 32 or the 4th adsorption tower 34, in analysis portion 4, analyze methane concentration and oxygen concentration.Based on the analytical results obtained by this analysis portion 4, vaporization rate when the liquid ammonia of deriving from the 2nd adsorption tower 32 or the 4th adsorption tower 34 gasifies by aftermentioned gasifier 5 can be set.
Derive and the liquid ammonia be supplied to the 10th pipe arrangement 90 or to derive and the liquid ammonia be supplied to the 10th pipe arrangement 90 flows through the 10th pipe arrangement 90 and is imported in gasifier 5 from the 4th adsorption tower 34 from the 2nd adsorption tower 32.
The liquid ammonia of deriving from the 2nd adsorption tower 32 or the 4th adsorption tower 34 carries out gasifying with the vaporization rate of regulation and is separated into gas phase composition and liquid composition by gasifier 5, thus lower-boiling impurity lower than ammonia for boiling point is removed with the isolated in form of gas phase composition, obtain the ammonia liquor after refining with the form of liquid composition.
In present embodiment, the liquid ammonia of deriving from the 2nd adsorption tower 32 or the 4th adsorption tower 34 carries out gasifying with the vaporization rate of 5 ~ 20 volume % based on the analytical results obtained by analysis portion 4 and is separated into gas phase composition and liquid composition by gasifier 5.In this case, 5 ~ 20 volume % of the liquid ammonia of deriving from the 2nd adsorption tower 32 or the 4th adsorption tower 34 are gas phase composition, and 80 ~ 95 volume % are liquid composition.
Specifically, gasifier 5 is when the concentration of at least one during the analytical results obtained by analysis portion 4 is methane and oxygen is lower than 30ppb, vaporization rate is set as 5 volume %, the concentration of at least one in methane and oxygen be more than 30ppb and lower than 50ppb, vaporization rate is set as 10 volume %, the concentration of at least one in methane and oxygen be more than 50ppb and lower than 100ppb, vaporization rate is set as 15 volume %, the concentration of at least one in methane and oxygen is more than 100ppb, vaporization rate is set as 20 volume %.
In the Ammonia purification system 100 of present embodiment, gasifier 5 will be eliminated oil content, be carried out gasifying by the liquid ammonia after high-boiling-point impurity adsorption section 3 absorption eliminates the high-boiling-point impurity such as moisture, higher hydrocarbon and be separated into gas phase composition and liquid composition with the vaporization rate of regulation by oil adsorption tower 2 absorption, therefore the lower-boiling impurities such as low-boiling point gas such as the lower hydrocarbon such as methane, ethane, propane and hydrogen, nitrogen, oxygen, argon gas, carbon monoxide can be removed with the isolated in form of gas phase composition, obtain the ammonia liquor after refining with the form of liquid composition.Therefore, the Ammonia purification system 100 of present embodiment can be refined ammonia by the method simplified when not carrying out the distillation along with backflow as conventional art, and can suppress the consumption of energy thus effectively refine ammonia.
In addition, as the gasification condition in gasifier 5, as long as the liquid ammonia of deriving from the 2nd adsorption tower 32 or the 4th adsorption tower 34 carries out the condition that gasifies just with the vaporization rate of regulation, do not limit, can suitably design temperature, pressure and time.In present embodiment, gasifier 5 is preferably separated into gas phase composition and liquid composition mode to be carried out gasifying at the temperature of-50 ~ 30 DEG C by the liquid ammonia of deriving from the 2nd adsorption tower 32 or the 4th adsorption tower 34 is formed.Thus, the liquid ammonia after absorption is eliminated oil content and high-boiling-point impurity gasifies effectively, thus can obtain being separated the ammonia liquor after eliminating lower-boiling impurity, and can improve the purity of this ammonia liquor.Temperature when gasifying to the liquid ammonia in gasifier 5 is lower than-50 DEG C, carrying out cooling needs a large amount of energy, therefore not preferred; Temperature when gasifying to the liquid ammonia in gasifier 5 is more than 30 DEG C, the impurity concentration contained in the ammonia liquor obtained with the form of liquid composition increases, therefore not preferred.
In addition, the preferred mode being separated into gas phase composition and liquid composition to be carried out gasifying under the pressure of 0.1 ~ 1.0MPa by the liquid ammonia of deriving from the 2nd adsorption tower 32 or the 4th adsorption tower 34 of gasifier 5 is formed.Pressure when gasifying to the liquid ammonia in gasifier 5 is lower than 0.1MPa, the temperature of ammonia is reduced, therefore carrying out cooling needs a large amount of energy, thus not preferred; Pressure when gasifying to the liquid ammonia in gasifier 5 is more than 1.0MPa, the temperature of ammonia is raised, the impurity concentration therefore contained in the ammonia liquor obtained with the form of liquid composition improves, thus not preferred.
In gasifier 5, the 11st pipe arrangement 91 being provided with the 11st valve 911 is connected with the 12nd pipe arrangement 92 being provided with the 12nd valve 921.It should be noted that, the 12nd pipe arrangement 92 is connected between gasifier 5 and withdrawing can 6.
In gasifier 5, under the state that the 11st valve 911 is opened, the lower-boiling impurity being separated removing with the form of gas phase composition from ammonia flows through the 11st pipe arrangement 91 and is discharged to its exterior.In addition, in gasifier 5, under the state that the 12nd valve 921 is opened, the ammonia liquor obtained with the form of liquid composition flows through the 12nd pipe arrangement 92 and is supplied in withdrawing can 6.
Withdrawing can 6 is stored in gasifier 5 with the ammonia liquor that the form of liquid composition obtains.This withdrawing can 6 preferably by temperature and pressure-controlling under constant conditions to make it possible to store with the form of ammonia liquor.
Fig. 2 is the figure of the formation of the Ammonia purification system 200 representing the 2nd embodiment of the present invention.The Ammonia purification system 200 of present embodiment is similar with above-mentioned Ammonia purification system 100, marks identical reference symbol, and omit the description the part of correspondence.Except the formation of high-boiling-point impurity adsorption section 201 is different from the formation of above-mentioned high-boiling-point impurity adsorption section 3, Ammonia purification system 200 is identical with Ammonia purification system 100.
The high-boiling-point impurity adsorption section 201 possessed in Ammonia purification system 200 will be derived from oil adsorption tower 2 and by the high-boiling-point impurity adsorbent removing by synthetic zeolite be made up of higher than ammonia of the boiling point that contains in the liquid ammonia of strainer 7.In present embodiment, comprise in the formation of high-boiling-point impurity adsorption section 201 as the 1st adsorption tower 2011 of multiple adsorption section, the 2nd adsorption tower 2012 and the 3rd adsorption tower 2013.
1st adsorption tower 2011, the 2nd adsorption tower 2012 and the 3rd adsorption tower 2013 have same formation with above-mentioned 1st adsorption tower 31.Specifically, in the 1st adsorption tower 2011, be filled with the 1st adsorption zone 20111 of MS-3A in the configuration of top of tower side, be filled with the 2nd adsorption zone 20112 of MS-13X in the configuration of tower bottom side.In the 2nd adsorption tower 2012, be filled with the 1st adsorption zone 20121 of MS-3A in the configuration of top of tower side, be filled with the 2nd adsorption zone 20122 of MS-13X in the configuration of tower bottom side.In the 3rd adsorption tower 2013, be filled with the 1st adsorption zone 20131 of MS-3A in the configuration of top of tower side, be filled with the 2nd adsorption zone 20132 of MS-13X in the configuration of tower bottom side.
In addition, in the Ammonia purification system 200 of present embodiment, the temperature of the 1st adsorption tower 2011, the 2nd adsorption tower 2012 and the 3rd adsorption tower 2013 is controlled as 0 ~ 60 DEG C, and pressure is controlled as 0.1 ~ 1.0MPa.When the temperature of the 1st adsorption tower 2011, the 2nd adsorption tower 2012 and the 3rd adsorption tower 2013 is lower than 0 DEG C, need the cooling carrying out the heat of adsorption produced during absorption removing impurity to be removed, thus energy efficiency likely reduces.When the temperature of the 1st adsorption tower 2011, the 2nd adsorption tower 2012 and the 3rd adsorption tower 2013 is more than 60 DEG C, the adsorptive power of sorbent material to impurity likely reduces.In addition, when the pressure of the 1st adsorption tower 2011, the 2nd adsorption tower 2012 and the 3rd adsorption tower 2013 is lower than 0.1MPa, the adsorptive power of sorbent material to impurity likely reduces.When the pressure of the 1st adsorption tower 2011, the 2nd adsorption tower 2012 and the 3rd adsorption tower 2013 is more than 1.0MPa, in order to maintain under a constant, need a large amount of energy, energy efficiency likely reduces.
In addition, the linear velocity in the 1st adsorption tower 2011, the 2nd adsorption tower 2012 and the 3rd adsorption tower 2013 is: the amount be supplied to by ammonia liquid in time per unit in each adsorption tower 2011,2012,2013 is converted into NTP(normal temperature and pressure) under gas volume and the value obtained divided by the void tower sectional area of each adsorption tower 2011,2012,2013 range preferably from 0.01 ~ 0.5m/ second.When on-line velocity is lower than 0.01m/ second, absorption removing impurity needs long-time, therefore not preferred; When on-line velocity is more than 0.5m/ second, the heat of adsorption produced during absorption removing impurity is not fully removed, and the adsorptive power of sorbent material to impurity likely reduces.
In addition, in present embodiment, deriving from oil adsorption tower 2 and be connected with from the 3rd pipe arrangement 83 branch the 13rd pipe arrangement 202, the 14th pipe arrangement 203 and the 15th pipe arrangement 204 out by the 3rd pipe arrangement 83 that the liquid ammonia of strainer 7 flows through.
13rd pipe arrangement 202 from the 3rd pipe arrangement 83 branch out and be connected with the top of tower of the 1st adsorption tower 2011.The 13rd valve 2021 of the stream opened or closed in the 13rd pipe arrangement 202 is provided with in the 13rd pipe arrangement 202.14th pipe arrangement 203 from the 3rd pipe arrangement 83 branch out and be connected with the top of tower of the 2nd adsorption tower 2012.The 14th valve 2031 of the stream opened or closed in the 14th pipe arrangement 203 is provided with in the 14th pipe arrangement 203.15th pipe arrangement 204 from the 3rd pipe arrangement 83 branch out and be connected with the top of tower of the 3rd adsorption tower 2013.The 105th valve 2041 of the stream opened or closed in the 15th pipe arrangement 204 is provided with in the 15th pipe arrangement 204.
In addition, the 16th pipe arrangement 205 flow through from the liquid ammonia of the 1st adsorption tower 2011 derivation is connected with at the tower bottom of the 1st adsorption tower 2011.The 16th valve 2051 of the stream opened or closed in the 16th pipe arrangement 205 is provided with in the 16th pipe arrangement 205.The 17th pipe arrangement 206 flow through from the liquid ammonia of the 2nd adsorption tower 2012 derivation is connected with at the tower bottom of the 2nd adsorption tower 2012.The 17th valve 2061 of the stream opened or closed in the 17th pipe arrangement 206 is provided with in the 17th pipe arrangement 206.The 18th pipe arrangement 207 flow through from the liquid ammonia of the 3rd adsorption tower 2013 derivation is connected with at the tower bottom of the 3rd adsorption tower 2031.The 18th valve 2071 of the stream opened or closed in the 18th pipe arrangement 207 is provided with in the 18th pipe arrangement 207.
In addition, the 16th pipe arrangement 205 is connected with from the 16th pipe arrangement 205 branch the 19th pipe arrangement 208 out.19th pipe arrangement 208 from the 16th pipe arrangement 205 branch out and be connected with the 14th pipe arrangement 203, becomes the stream for being imported to by the liquid ammonia of deriving from the 1st adsorption tower 2011 in the 2nd adsorption tower 2012.The 19th valve 2081 of the stream of opening or closing in the 19th pipe arrangement 208 is provided with in the 19th pipe arrangement 208.19th pipe arrangement 208 is connected with from the 19th pipe arrangement 208 branch the 20th pipe arrangement 209 out.20th pipe arrangement 209 from the 19th pipe arrangement 208 branch out and be connected with the 15th pipe arrangement 204, becomes the stream for being imported to by the liquid ammonia of deriving from the 1st adsorption tower 2011 in the 3rd adsorption tower 2013.The 20th valve 2091 of the stream of opening or closing in the 20th pipe arrangement 209 is provided with in the 20th pipe arrangement 209.
In addition, the 17th pipe arrangement 206 is connected with from the 17th pipe arrangement 206 branch the 21st pipe arrangement 210 out and the 22nd pipe arrangement 211.21st pipe arrangement 210 from the 17th pipe arrangement 206 branch out and be connected with the 13rd pipe arrangement 202, becomes the stream for being imported to by the liquid ammonia of deriving from the 2nd adsorption tower 2012 in the 1st adsorption tower 2011.The 21st valve 2101 of the stream of opening or closing in the 21st pipe arrangement 210 is provided with in the 21st pipe arrangement 210.22nd pipe arrangement 211 from the 17th pipe arrangement 206 branch out and be connected with the 15th pipe arrangement 204, becomes the stream for being imported to by the liquid ammonia of deriving from the 2nd adsorption tower 2012 in the 3rd adsorption tower 2013.The 22nd valve 2111 of the stream of opening or closing in the 22nd pipe arrangement 211 is provided with in the 22nd pipe arrangement 211.
In addition, the 18th pipe arrangement 207 is connected with from the 18th pipe arrangement 207 branch the 23rd pipe arrangement 212 out.23rd pipe arrangement 212 from the 18th pipe arrangement 207 branch out and be connected with the 13rd pipe arrangement 202, becomes the stream for being imported to by the liquid ammonia of deriving from the 3rd adsorption tower 2013 in the 1st adsorption tower 2011.The 23rd valve 2121 of the stream of opening or closing in the 23rd pipe arrangement 212 is provided with in the 23rd pipe arrangement 212.23rd pipe arrangement 212 is connected with from the 23rd pipe arrangement 212 branch the 24th pipe arrangement 213 out.24th pipe arrangement 213 from the 23rd pipe arrangement 212 branch out and be connected with the 14th pipe arrangement 203, becomes the stream for being imported to by the liquid ammonia of deriving from the 3rd adsorption tower 2013 in the 2nd adsorption tower 2012.The 24th valve 2131 of the stream of opening or closing in the 24th pipe arrangement 213 is provided with in the 24th pipe arrangement 213.
In addition, for the 16th pipe arrangement 205, the 17th pipe arrangement 206 and the 18th pipe arrangement 207, connect the 25th pipe arrangement 214 in the direction end of downstream side that flows through of liquid ammonia.The liquid ammonia of deriving from any one adsorption tower the 1st adsorption tower 2011, the 2nd adsorption tower 2012 and the 3rd adsorption tower 2013 is supplied in the 25th pipe arrangement 214.In addition, the 10th pipe arrangement 90 being provided with the 8th pipe arrangement 88 out and with analysis portion 4 be connected from the 25th pipe arrangement 214 branch and out and with gasifier 5 being connected from the 25th pipe arrangement 214 branch in the 25th pipe arrangement 214.
According in the Ammonia purification system 200 formed as mentioned above, about the connection of the 1st adsorption tower 2011, the 2nd adsorption tower 2012 and the 3rd adsorption tower 2013, there are following six kinds of connection modes.
1st kind of connection mode is make to derive and by the liquid ammonia of strainer 7 successively by the connection mode of the 1st adsorption tower 2011, the 2nd adsorption tower 2012 from oil adsorption tower 2.In the 1st kind of connection mode, 13rd valve 2021, the 17th valve 2061 and the 19th valve 2081 are opened, the 14th valve 2031, the 15th valve 2041, the 16th valve 2051, the 18th valve 2071, the 20th valve 2091, the 21st valve 2101, the 22nd valve 2111, the 23rd valve 2121 and the 24th valve 2131 are closed.Thus, derive from oil adsorption tower 2 and flow through the 13rd pipe arrangement 202 by the liquid ammonia of strainer 7 and import to the 1st adsorption tower 2011, the liquid ammonia of deriving from the 1st adsorption tower 2011 flows through the 16th pipe arrangement 205 and the 19th pipe arrangement 208 and imports to the 2nd adsorption tower 2012, flow through the 17th pipe arrangement 206 from the liquid ammonia of the 2nd adsorption tower 2012 derivation and be supplied to the 25th pipe arrangement 214, liquid ammonia imports to analysis portion 4 and gasifier 5 from the 25th pipe arrangement 214.In the such the 1st kind of connection mode, the high-boiling-point impurity contained in the liquid ammonia of removing can be adsorbed in the 1st adsorption tower 2011 and the 2nd adsorption tower 2012, therefore, it is possible to improve the absorption removing ability to high-boiling-point impurity.In addition, in the 1st kind of connection mode, do not carry out the absorption removing operation in the 3rd adsorption tower 2013, therefore can carry out manipulation of regeneration to the 3rd adsorption tower 2013.
2nd kind of connection mode is make to derive and by the liquid ammonia of strainer 7 successively by the connection mode of the 1st adsorption tower 2011, the 3rd adsorption tower 2013 from oil adsorption tower 2.In the 2nd kind of connection mode, 13rd valve 2021, the 18th valve 2071 and the 20th valve 2091 are opened, the 14th valve 2031, the 15th valve 2041, the 16th valve 2051, the 17th valve 2061, the 19th valve 2081, the 21st valve 2101, the 22nd valve 2111, the 23rd valve 2121 and the 24th valve 2131 are closed.Thus, derive from oil adsorption tower 2 and flow through the 13rd pipe arrangement 202 by the liquid ammonia of strainer 7 and import to the 1st adsorption tower 2011, flow through the 16th pipe arrangement 205, the 19th pipe arrangement 208 and the 20th pipe arrangement 209 from the liquid ammonia of the 1st adsorption tower 2011 derivation and import to the 3rd adsorption tower 2013, flow through the 18th pipe arrangement 207 from the liquid ammonia of the 3rd adsorption tower 2013 derivation and be supplied to the 25th pipe arrangement 214, liquid ammonia imports to analysis portion 4 and gasifier 5 from the 25th pipe arrangement 214.In the such the 2nd kind of connection mode, the high-boiling-point impurity contained in the liquid ammonia of removing can be adsorbed in the 1st adsorption tower 2011 and the 3rd adsorption tower 2013, therefore, it is possible to improve the absorption removing ability to high-boiling-point impurity.In addition, in the 2nd kind of connection mode, do not carry out the absorption removing operation in the 2nd adsorption tower 2012, therefore can carry out manipulation of regeneration to the 2nd adsorption tower 2012.
3rd kind of connection mode is make to derive and by the liquid ammonia of strainer 7 successively by the connection mode of the 2nd adsorption tower 2012, the 1st adsorption tower 2011 from oil adsorption tower 2.In the 3rd kind of connection mode, 14th valve 2031, the 16th valve 2051 and the 21st valve 2101 are opened, the 13rd valve 2021, the 15th valve 2041, the 17th valve 2061, the 18th valve 2071, the 19th valve 2081, the 20th valve 2091, the 22nd valve 2111, the 23rd valve 2121 and the 24th valve 2131 are closed.Thus, derive from oil adsorption tower 2 and flow through the 14th pipe arrangement 203 by the liquid ammonia of strainer 7 and import to the 2nd adsorption tower 2012, the liquid ammonia of deriving from the 2nd adsorption tower 2012 flows through the 17th pipe arrangement 206 and the 21st pipe arrangement 210 and imports to the 1st adsorption tower 2011, flow through the 16th pipe arrangement 205 from the liquid ammonia of the 1st adsorption tower 2011 derivation and be supplied to the 25th pipe arrangement 214, liquid ammonia imports to analysis portion 4 and gasifier 5 from the 25th pipe arrangement 214.In the such the 3rd kind of connection mode, the high-boiling-point impurity contained in the liquid ammonia of removing can be adsorbed in the 1st adsorption tower 2011 and the 2nd adsorption tower 2012, therefore, it is possible to improve the absorption removing ability to impurity.In addition, in the 3rd kind of connection mode, do not carry out the absorption removing operation in the 3rd adsorption tower 2013, therefore can carry out manipulation of regeneration to the 3rd adsorption tower 2013.
4th kind of connection mode is make to derive and by the liquid ammonia of strainer 7 successively by the connection mode of the 2nd adsorption tower 2012, the 3rd adsorption tower 2013 from oil adsorption tower 2.In the 4th kind of connection mode, 14th valve 2031, the 18th valve 2071 and the 22nd valve 2111 are opened, the 13rd valve 2021, the 15th valve 2041, the 16th valve 2051, the 17th valve 2061, the 19th valve 2081, the 20th valve 2091, the 21st valve 2101, the 23rd valve 2121 and the 24th valve 2131 are closed.Thus, derive from oil adsorption tower 2 and flow through the 14th pipe arrangement 203 by the liquid ammonia of strainer 7 and import to the 2nd adsorption tower 2012, the liquid ammonia of deriving from the 2nd adsorption tower 2012 flows through the 17th pipe arrangement 206 and the 22nd pipe arrangement 211 and imports to the 3rd adsorption tower 2013, flow through the 18th pipe arrangement 207 from the liquid ammonia of the 3rd adsorption tower 2013 derivation and be supplied to the 25th pipe arrangement 214, liquid ammonia imports to analysis portion 4 and gasifier 5 from the 25th pipe arrangement 214.In the such the 4th kind of connection mode, the high-boiling-point impurity contained in the liquid ammonia of removing can be adsorbed in the 2nd adsorption tower 2012 and the 3rd adsorption tower 2013, therefore, it is possible to improve the absorption removing ability to high-boiling-point impurity.In addition, in the 4th kind of connection mode, do not carry out the absorption removing operation in the 1st adsorption tower 2011, therefore can carry out manipulation of regeneration to the 1st adsorption tower 2011.
5th kind of connection mode is make to derive and by the liquid ammonia of strainer 7 successively by the connection mode of the 3rd adsorption tower 2013, the 1st adsorption tower 2011 from oil adsorption tower 2.In the 5th kind of connection mode, 15th valve 2041, the 16th valve 2051 and the 23rd valve 2121 are opened, the 13rd valve 2021, the 14th valve 2031, the 17th valve 2061, the 18th valve 2071, the 19th valve 2081, the 20th valve 2091, the 21st valve 2101, the 22nd valve 2111 and the 24th valve 2131 are closed.Thus, derive from oil adsorption tower 2 and flow through the 15th pipe arrangement 204 by the liquid ammonia of strainer 7 and import to the 3rd adsorption tower 2013, the liquid ammonia of deriving from the 3rd adsorption tower 2013 flows through the 18th pipe arrangement 207 and the 23rd pipe arrangement 212 and imports to the 1st adsorption tower 2011, flow through the 16th pipe arrangement 205 from the liquid ammonia of the 1st adsorption tower 2011 derivation and be supplied to the 25th pipe arrangement 214, liquid ammonia imports to analysis portion 4 and gasifier 5 from the 25th pipe arrangement 214.In the such the 5th kind of connection mode, the high-boiling-point impurity contained in the liquid ammonia of removing can be adsorbed in the 1st adsorption tower 2011 and the 3rd adsorption tower 2013, therefore, it is possible to improve the absorption removing ability to high-boiling-point impurity.In addition, in the 5th kind of connection mode, do not carry out the absorption removing operation in the 2nd adsorption tower 2012, therefore can carry out manipulation of regeneration to the 2nd adsorption tower 2012.
6th kind of connection mode is make to derive and by the liquid ammonia of strainer 7 successively by the connection mode of the 3rd adsorption tower 2013, the 2nd adsorption tower 2012 from oil adsorption tower 2.In the 6th kind of connection mode, 15th valve 2041, the 17th valve 2061 and the 24th valve 2131 are opened, the 13rd valve 2021, the 14th valve 2031, the 16th valve 2051, the 18th valve 2071, the 19th valve 2081, the 20th valve 2091, the 21st valve 2101, the 22nd valve 2111 and the 23rd valve 2121 are closed.Thus, derive from oil adsorption tower 2 and flow through the 15th pipe arrangement 204 by the liquid ammonia of strainer 7 and import to the 3rd adsorption tower 2013, flow through the 18th pipe arrangement 207, the 23rd pipe arrangement 212 and the 24th pipe arrangement 213 from the liquid ammonia of the 3rd adsorption tower 2013 derivation and import to the 2nd adsorption tower 2012, flow through the 17th pipe arrangement 206 from the liquid ammonia of the 2nd adsorption tower 2012 derivation and be supplied to the 25th pipe arrangement 214, liquid ammonia imports to analysis portion 4 and gasifier 5 from the 25th pipe arrangement 214.In the such the 6th kind of connection mode, the high-boiling-point impurity contained in the liquid ammonia of removing can be adsorbed in the 2nd adsorption tower 2012 and the 3rd adsorption tower 2013, therefore, it is possible to improve the absorption removing ability to high-boiling-point impurity.In addition, in the 6th kind of connection mode, do not carry out the absorption removing operation in the 1st adsorption tower 2011, therefore can carry out manipulation of regeneration to the 1st adsorption tower 2011.
The present invention can implement in other various modes when not departing from its spirit or principal character.Therefore, above-mentioned embodiment is only simply illustrate all respects, and scope of the present invention is the scope shown in claims, not by any constraint of specification sheets.In addition, belong to the distortion of claims and change all within the scope of the present invention.
Nomenclature
1 hold tank
2 oil adsorption tower
3 high-boiling-point impurity adsorption sections
4 analysis portion
5 gasifiers
6 withdrawing cans
31,2011 the 1st adsorption towers
32,2012 the 2nd adsorption towers
33,2013 the 3rd adsorption towers
34 the 4th adsorption towers
100,200 Ammonia purification system
311,321,331,341,20111,20121,20131 the 1st adsorption zones
312,322,332,342,20112,20122,20132 the 2nd adsorption zones
Claims (6)
1. an Ammonia purification system, it is the Ammonia purification system of refining the thick ammonia containing impurity, it is characterized in that, comprises:
Reservoir, the thick ammonia of its storing liquid shape;
1st adsorption section, the oil content contained in the liquid thick ammonia stored in described reservoir is removed by charcoal absorption by it, the ammonia of tapping shape;
2nd adsorption section, high-boiling-point impurity higher than ammonia for the boiling point contained in the liquid ammonia of deriving from described 1st adsorption section is removed by synthetic zeolite absorption by it, the ammonia of tapping shape, wherein, described 2nd adsorption section has: be filled with as the MS-3A of synthetic zeolite the 1st adsorption zone and be filled with the 2nd adsorption zone of the MS-13X as synthetic zeolite, the temperature of described 2nd adsorption section is controlled as 0 ~ 60 DEG C, pressure is controlled as 0.1 ~ 1.0MPa; With
Gasification portion, the liquid ammonia of deriving from described 2nd adsorption section carries out gasifying with the vaporization rate of regulation and is separated into gas phase composition and liquid composition by it, thus lower-boiling impurity lower than ammonia for boiling point is removed with the isolated in form of gas phase composition, obtain the ammonia liquor after refining with the form of liquid composition.
2. Ammonia purification system according to claim 1, is characterized in that, also comprises the analysis portion analyzed the concentration of the impurity contained in the liquid ammonia of deriving from described 2nd adsorption section,
Described gasification portion sets the vaporization rate of described regulation when being gasified by the liquid ammonia of deriving from described 2nd adsorption section based on the analytical results that described analysis portion obtains.
3. Ammonia purification system according to claim 2, is characterized in that, the vaporization rate of described regulation when gasifying to the liquid ammonia of deriving from described 2nd adsorption section is set as 5 ~ 20 volume % by described gasification portion.
4. the Ammonia purification system according to any one of claims 1 to 3, is characterized in that, the liquid ammonia of deriving from described 2nd adsorption section carries out gasifying and is separated into gas phase composition and liquid composition by described gasification portion at the temperature of-50 ~ 30 DEG C.
5. the Ammonia purification system according to any one of claims 1 to 3, it is characterized in that, described 2nd adsorption section has multiple adsorption sections connected in series or in parallel, the high-boiling-point impurity absorption removing that the plurality of adsorption section will be contained in the liquid ammonia of deriving from described 1st adsorption section.
6. a process for purification for ammonia, it is the method for refining the thick ammonia containing impurity, it is characterized in that, comprises:
Storage operation, the wherein thick ammonia of storing liquid shape;
1st absorption process, is wherein removed the oil content contained in the liquid thick ammonia stored in described storage operation by charcoal absorption;
2nd absorption process, wherein using high-boiling-point impurity higher than ammonia for the boiling point that contains in the liquid ammonia after absorption eliminates oil content in described 1st absorption process under temperature is 0 ~ 60 DEG C and pressure is the condition of 0.1 ~ 1.0MPa by MS-3A and the MS-13X absorption removing as synthetic zeolite; With
Gasification process, wherein the liquid ammonia after absorption eliminates high-boiling-point impurity in described 2nd absorption process is carried out gasifying with the vaporization rate of regulation and is separated into gas phase composition and liquid composition, thus lower-boiling impurity lower than ammonia for boiling point is removed with the isolated in form of gas phase composition, obtain the ammonia liquor after refining with the form of liquid composition.
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| JP2011013499 | 2011-01-25 | ||
| JP2011-013499 | 2011-01-25 | ||
| PCT/JP2011/079106 WO2012101925A1 (en) | 2011-01-25 | 2011-12-15 | Ammonia purification system and method for purifying ammonia |
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| CN103153861B true CN103153861B (en) | 2015-04-22 |
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| JP (1) | JP5738900B2 (en) |
| KR (1) | KR101570392B1 (en) |
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| JP6082914B2 (en) * | 2012-08-16 | 2017-02-22 | 日本パイオニクス株式会社 | Ammonia purification method |
| JP2014047089A (en) * | 2012-08-30 | 2014-03-17 | Japan Pionics Co Ltd | Apparatus for feeding purified ammonia |
| JP6142152B2 (en) * | 2012-09-21 | 2017-06-07 | 日本パイオニクス株式会社 | Oil content measuring apparatus and oil content measuring method |
| JP2016188154A (en) * | 2015-03-30 | 2016-11-04 | 大陽日酸株式会社 | Method for purifying ammonia |
| WO2018055971A1 (en) * | 2016-09-26 | 2018-03-29 | 住友精化株式会社 | Method for purifying hydrogen or helium, and device for purifying hydrogen or helium |
| CN106673013B (en) * | 2016-11-17 | 2018-10-09 | 天津大学 | The reprocessing process and system of unqualified liquefied ammonia in refinery(waste) water production |
| CN110671602A (en) * | 2018-07-03 | 2020-01-10 | 山东恒昌圣诚化工股份有限公司 | Self-heating type solid ammonia filling device |
| CN110015668A (en) * | 2019-04-02 | 2019-07-16 | 巫协森 | Primary liquefied ammonia purifying is the method and its system of high purity liquid ammonia |
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2011
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Also Published As
| Publication number | Publication date |
|---|---|
| KR101570392B1 (en) | 2015-11-19 |
| JP5738900B2 (en) | 2015-06-24 |
| WO2012101925A1 (en) | 2012-08-02 |
| TW201231385A (en) | 2012-08-01 |
| KR20130140658A (en) | 2013-12-24 |
| CN103153861A (en) | 2013-06-12 |
| TWI491558B (en) | 2015-07-11 |
| JPWO2012101925A1 (en) | 2014-06-30 |
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