CN110395746A - A kind of device and method of liquefied ammonia refinery decolorization - Google Patents
A kind of device and method of liquefied ammonia refinery decolorization Download PDFInfo
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- CN110395746A CN110395746A CN201910767940.6A CN201910767940A CN110395746A CN 110395746 A CN110395746 A CN 110395746A CN 201910767940 A CN201910767940 A CN 201910767940A CN 110395746 A CN110395746 A CN 110395746A
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- ammonia
- liquefied 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
- C01C1/024—Purification
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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
Abstract
The present invention relates to ammonia refining technical fields, more particularly, to a kind of device and method of liquefied ammonia refinery decolorization.Described device, including sequentially connected clean unit, ammonia gas finisher, segregator, crystallizer, preheater, fine de-sulfur device, ammonium hydroxide preparing tank, rectifying column, decoloration unit and liquefied ammonia surge tank；The liquefied ammonia surge tank is also connected with the segregator；The discharge end of the ammonium hydroxide preparing tank is connected by heat exchanger with the feed end of the rectifying column；The ammonia gas finisher is for contacting thick ammonia with concentrated ammonia liquor to remove H2S；Contain desulphurization catalyst in the fine de-sulfur device.Described method includes following steps: thick ammonia obtains liquefied ammonia through preliminary purification processing, with concentrated ammonia liquor contact treating, fractional condensation water removal, crystallization desulfurization and fine de-sulfur processing, rectifying, decoloration.Using apparatus and method of the present invention, impurity content in liquefied ammonia can reduce, obtain the colourless liquefied ammonia product of high quality.
Description
Technical field
The present invention relates to ammonia refining technical fields, more particularly, to a kind of device and method of liquefied ammonia refinery decolorization.
Background technique
For oil plant during Sulfur-Containing Crude, the devices such as Atmospheric vacuum, catalytic cracking, reformation plus hydrogen can generate acid dirt
Water, the sour water contain a large amount of ammonia and hydrogen sulfide, therefore before sour water is discharged into sewage treatment plant, need to carry out pre-
Processing, domestic refinery generallys use vaporizing extract process and isolates ammonia and hydrogen sulfide, and the thick ammonia being stripped off then is removed by technology for refining ammonia
Devulcanization hydrogen impurity, the liquefied ammonia product of by-product high added value.
Liquefied ammonia, which contains impurity, causes liquefied ammonia to change colour, and liquefied ammonia impurities are mostly the Fe of free state2+、H2S, phenols, light oil,
Mercaptan, water and chloride ion.Fe2+In light green color, Fe can be oxidized to3+In brown color, phenols can be oxidized to red quinones object
Matter, the molysite of phenol are similarly red, and mercaptan has stink.Fe in liquefied ammonia2+Be from stripper plant containing acid water and
The H of lateral line withdrawal function system carbon steel material2S corrosion, subsequent ammonia refining device mostly use stainless steel material, low operation temperature, H2S
Likelihood of corrosion is small；Light oil, chloride ion, phenols and water are carried secretly from the stripping of acid water；Light oil constituents is lighter, ammonia compressor outlet
Temperature is higher, is difficult to separate with ammonia；H2S and mercaptan come from acid water, and the latter is not easy to remove in concentrated ammonia liquor circulation washing.Liquid
The critical impurities of ammonia discoloration are the Fe of free state2+And phenols, the impurity of hardly possible removing is light oil and mercaptan.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of device of liquefied ammonia refinery decolorization, existing in the prior art to solve
Liquefied ammonia containing it is miscellaneous, discoloration the technical issues of.
The second object of the present invention is to provide a kind of method of liquefied ammonia refinery decolorization, can reduce impurity in liquefied ammonia and contain
Amount, obtains the colourless liquefied ammonia product of high quality.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of device of liquefied ammonia refinery decolorization, including sequentially connected clean unit, ammonia gas finisher, segregator, crystallizer,
Preheater, fine de-sulfur device, ammonium hydroxide preparing tank, rectifying column, decoloration unit and liquefied ammonia surge tank；
The liquefied ammonia surge tank is also connected with the segregator；
The discharge end of the ammonium hydroxide preparing tank is connected by heat exchanger with the feed end of the rectifying column；
The ammonia gas finisher is for contacting thick ammonia with concentrated ammonia liquor to remove H2S；
Contain desulphurization catalyst in the fine de-sulfur device.
The device of liquefied ammonia refinery decolorization of the invention, is arranged clean unit before ammonia gas finisher, removes the portion in thick ammonia
Divide organic impurities, moisture and solid impurity, reduces its influence to the concentration and temperature of cyclic ammonia water；In ammonia gas finisher, slightly
Ammonia and concentrated ammonia liquor come into full contact with (preferably counter current contacting), make major part H therein2S is washed to be absorbed into ammonium hydroxide, realization pair
The preliminary purification of thick ammonia；The moisture of entrainment is isolated by segregator, then makes impurity crystallization in multilayer crystallization plates by crystallizer
On, realize the further purification to ammonia；In fine de-sulfur device, H2S reaction under desulphurization catalyst effect generates other materials
It rests in the catalyst bed of fine de-sulfur device, guarantees H2S content≤10ppm；Ammonia after fine de-sulfur is mixed with weak aqua ammonia
To concentrated ammonia liquor, it is sent into rectifying column after heat exchanger adjusts temperature and carries out rectifying, it is single that tower top discharge high concentration ammonia enters decoloration
In member, product feeding liquefied ammonia surge tank is obtained after carrying out decolorization.
Wherein, the desulphurization catalyst of conventional ammonia refining process can be used in the desulphurization catalyst in fine de-sulfur device.
In an of the invention preferred embodiment, the decoloration unit includes shell, shell it is interior by activated carbon fiber layers every
From circulation chamber and transition chamber is formed, the circulation chamber is isolated by baffle forms feed space and discharge chamber；The feed space with it is described
Rectifying column is connected, and the discharge chamber is connected with the liquefied ammonia surge tank.
Optionally, described device includes at least two decoloration units.It is arranged in parallel between each decoloration unit, one opens one
It is standby, regeneration can be switched in time.
The decoloration unit that the present invention is arranged using the above structure, ammonia, can with activated carbon fiber layers in decoloration unit
The impurity such as the organic matter of the contact removing adsorption of cross-flow twice, obtain the liquefied ammonia product of high quality.
Optionally, the feed end of the decoloration unit is provided with ammonia entrance；It is additionally provided with regeneration steam outlet.It is described
The discharge end of decoloration unit is provided with ammonia outlet；It is additionally provided with regeneration steam entry.Each outlet is provided with valve and is used for
Regulate and control open and-shut mode and flow etc..
It include: that regeneration treatment is carried out using 0.78MPa, 169 DEG C of vapor using the regenerated condition of vapor.
As in different embodiments, the shell of the decoloration unit can be regular global shell, square shell, cylindrical shell
Body etc., or other irregular shells.
Activated carbon fiber layers in decoloration unit can be an independent activated carbon fiber layers, be enclosed circulation chamber；Decoloration
Unit is also possible to more than one activated carbon fiber layers, is connected to each other and is enclosed circulation chamber.
In a preferred embodiment of the invention, the charging at the bottom discharge end of the rectifying column and the ammonium hydroxide preparing tank
End is connected.
The bottom discharge end of rectifying column is connected with the feed end of ammonium hydroxide preparing tank, can provide dilute ammonia for ammonium hydroxide preparing tank
Water.
In a preferred embodiment of the invention, the bottom discharge end of the rectifying column is matched by heat exchanger and the ammonium hydroxide
The feed end of tank processed is connected.The weak aqua ammonia temperature that rectifier bottoms are discharged is adjusted by heat exchanger, makes to prepare in ammonium hydroxide
Suitable temperature is obtained in tank.
In a preferred embodiment of the invention, the ammonia gas finisher is circumscribed with ammonia circulation pump.Specifically, the ammonia essence
The bottom discharge end of device processed is pumped by the ammonia circulation to be connected with the top feed end of the ammonia gas finisher.
Ammonium hydroxide is pumped by ammonia circulation and is delivered at the top of ammonia gas finisher by ammonia gas finisher bottom cycle, realizes circulation ammonia refining
Process.
In a preferred embodiment of the invention, the clean unit is connected with the bottom feed end of the ammonia gas finisher.
Wherein, the clean unit can be active carbon purifying unit.
From ammonia gas finisher bottom into the ammonia through activated carbon adsorption, it can come into full contact with, send out with the concentrated ammonia liquor adverse current of circulation
Raw following reaction: NH3·H2O+H2S→NH4HS+H2O, 2NH3·H2O+H2S→(NH4)2S+2H2O, the H of wherein most2S quilt
Washing absorption realizes the preliminary removing H of thick ammonia into cyclic ammonia water2S。
In a preferred embodiment of the invention, the liquefied ammonia surge tank is connected with the ammonia gas finisher.
Liquefied ammonia in liquefied ammonia surge tank is delivered in ammonia gas finisher, provides concentrated ammonia liquor, make ammonia carry out wherein it is cooling and
Purification.
In a preferred embodiment of the invention, the decoloration unit is connected by condenser with the liquefied ammonia surge tank.
Ammonia through the unit that decolourizes is condensed through condenser, obtains the liquefied ammonia product of high quality.
In a preferred embodiment of the invention, the discharge end of the ammonium hydroxide preparing tank passes through heat exchanger, surge tank and institute
The feed end for stating rectifying column is connected.
Optionally, described device includes at least two active carbon purifying units.It is in parallel between each active carbon purifying unit
Setting, one opens one standby, can switch regeneration in time.
The present invention also provides a kind of methods of liquefied ammonia refinery decolorization, include the following steps:
Thick ammonia is handled through preliminary purification, is handled with concentrated ammonia liquor contact treating, fractional condensation water removal, crystallization desulfurization and fine de-sulfur, essence
It evaporates, decolourize to obtain liquefied ammonia.
By above-mentioned processing method, it is capable of handling to obtain the liquefied ammonia product of high quality.
Optionally, preliminary purification processing is carried out using active carbon.Remove most water, organic impurities and solid impurity
Deng.
Optionally, the condition of the purification include: in 0 DEG C~10 DEG C, 0.15MPa~0.25Mpa, contacted with concentrated ammonia liquor instead
It answers.Under the above conditions, following reaction: NH occurs3·H2O+H2S→NH4HS+H2O, 2NH3·H2O+H2S→(NH4)2S+2H2O,
So that most H in thick ammonia2S is washed to be absorbed into cyclic ammonia water, realizes the preliminary H of thick ammonia2S removing.
Optionally, the temperature of the fractional condensation water removal is 0 DEG C~10 DEG C.It is isolated at this temperature from subtractive process entrainment
Moisture.
Wherein, the method for crystallizing desulfurization includes: in -10 DEG C~0 DEG C progress crystallization treatment.Under the above conditions, by low
Warm desublimation, by NH4HS and (NH4)2S is crystallized on multilayer crystallization plates, realizes the further purification of ammonia.
Optionally, it is 45 DEG C~55 DEG C that the condition of the rectifying, which includes: tower top temperature, and column bottom temperature is 140 DEG C~150
DEG C, pressure is 1.4MPa~1.5MPa.
Optionally, decolorization is carried out using activated carbon adsorption fiber.
Compared with prior art, the invention has the benefit that
(1) in the device of the invention, clean unit is set before ammonia gas finisher, the part removed in thick ammonia is organic miscellaneous
Matter, moisture and solid impurity reduce its influence to the concentration and temperature of cyclic ammonia water；In ammonia gas finisher, thick ammonia with it is dense
Ammonium hydroxide adverse current comes into full contact with, and makes major part H therein2S is washed to be absorbed into ammonium hydroxide；In fine de-sulfur device, H2It is raw after S reaction
It is rested at other materials in the catalyst bed of fine de-sulfur device, guarantees H2S content≤10ppm；
(2) the decoloration unit of specific structure of the present invention setting, ammonia, can two with activated carbon fiber layers in decoloration unit
The impurity such as the organic matter of secondary cross-flow contact removing adsorption, obtain the liquefied ammonia product of high quality；
(3) using method of the invention, it is possible to reduce impurity content in liquefied ammonia, the colourless liquefied ammonia product of high quality is obtained.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the structural schematic diagram of the device of liquefied ammonia refinery decolorization provided in an embodiment of the present invention；
Fig. 2 is the cross section structure schematic diagram of decoloration unit provided in an embodiment of the present invention.
Appended drawing reference:
The first clean unit of 1-；The second clean unit of 2-；3- ammonia gas finisher；
4- ammonia circulation pump；5- segregator；6- crystallizer；
7- preheater；8- fine de-sulfur device；9- ammonium hydroxide preparing tank；
10- First Heat Exchanger；11- surge tank；The second heat exchanger of 12-；
13- rectifying column；The decoloration unit of 14- first；The decoloration unit of 15- second；
16- condenser；17- liquefied ammonia surge tank；141- shell；
142- activated carbon fiber layers；143- transition chamber；144- baffle；
145- feed space；146- discharge chamber；1451- ammonia entrance；
1452- regenerates steam entry；1461- ammonia outlet；1462- regenerates steam outlet.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that it is following described embodiments are some of the embodiments of the present invention, rather than it is whole
Embodiment is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same
Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
In the description of the present invention, it should be noted that term " center ", "upper", "lower", "left", "right", "vertical",
The orientation or positional relationship of the instructions such as "horizontal", "inner", "outside" be based on the orientation or positional relationship shown in the drawings, merely to
Convenient for description the present invention and simplify description, rather than the device or element of indication or suggestion meaning must have a particular orientation,
It is constructed and operated in a specific orientation, therefore is not considered as limiting the invention.In addition, term " first ", " second ",
" third " is used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance.
In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term " installation ", " phase
Even ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or be integrally connected；It can
To be mechanical connection, it is also possible to be electrically connected；It can be directly connected, can also can be indirectly connected through an intermediary
Connection inside two elements.For the ordinary skill in the art, above-mentioned term can be understood at this with concrete condition
Concrete meaning in invention.
Fig. 1 is the apparatus structure schematic diagram of liquefied ammonia refinery decolorization provided in an embodiment of the present invention.As shown in Figure 1, this implementation
The device for the liquefied ammonia refinery decolorization that example provides includes sequentially connected clean unit, ammonia gas finisher 3, segregator 5, crystallizer 6, pre-
Hot device 7, fine de-sulfur device 8, ammonium hydroxide preparing tank 9, rectifying column 13, decoloration unit and liquefied ammonia surge tank 17.The liquefied ammonia surge tank 17
Also it is connected with the segregator 5.The discharge end of the ammonium hydroxide preparing tank 9 passes through the feed end phase of heat exchanger and the rectifying column 13
Even.
Specifically, the discharge end of the ammonium hydroxide preparing tank 9 passes through the feed end of First Heat Exchanger 10 and the rectifying column 13
It is connected.
Further, the discharge end of the ammonium hydroxide preparing tank 9 passes sequentially through First Heat Exchanger 10, surge tank 11 and second changes
The feed end of hot device more than 12 rectifying column 13 is connected.
Further, the bottom discharge end of the rectifying column 13 is connected with the feed end of the ammonium hydroxide preparing tank 9.Rectifying column
13 bottom discharge end is connected with the feed end of ammonium hydroxide preparing tank 9, can provide weak aqua ammonia for ammonium hydroxide preparing tank 9.
Further, the bottom discharge end of the rectifying column 13 passes through the second heat exchanger 12 and the ammonium hydroxide preparing tank 9
Feed end is connected, and is adjusted by the weak aqua ammonia temperature that 13 bottom of rectifying column is discharged in the second heat exchanger 12, makes to match in ammonium hydroxide
Suitable temperature is obtained in tank 9 processed.
In a preferred embodiment of the invention, the ammonia gas finisher 3 is circumscribed with ammonia circulation pump 4.Specifically, the ammonia
The bottom discharge end of treater 3 is connected by ammonia circulation pump 4 with the top feed end of the ammonia gas finisher 3.Ammonium hydroxide is logical
It crosses ammonia circulation pump to be delivered at the top of ammonia gas finisher by ammonia gas finisher bottom cycle, realizes circulation ammonia refining process.
In a preferred embodiment of the invention, the clean unit is connected with the bottom feed end of the ammonia gas finisher 3.
From 3 bottom of ammonia gas finisher into the ammonia through activated carbon adsorption, it can come into full contact with, occur following anti-with the concentrated ammonia liquor adverse current of circulation
It answers: NH3·H2O+H2S→NH4HS+H2O, 2NH3·H2O+H2S→(NH4)2S+2H2O, the H of wherein most2S is washed to be absorbed
Into cyclic ammonia water, the preliminary removing H of thick ammonia is realized2S。
Optionally, described device includes more than two clean units, the first clean unit 1 and the second clean unit 2.Two
It is arranged in parallel between clean unit, one opens one standby, can switch regeneration in time.Specifically, the clean unit can be active carbon
Clean unit carries out purified treatment using active carbon.
Further, the liquefied ammonia surge tank 17 is connected with the ammonia gas finisher 3.Liquefied ammonia conveying in liquefied ammonia surge tank 17
Into ammonia gas finisher 3, concentrated ammonia liquor is provided, ammonia is made to be cooled down and be purified wherein.
Further, the decoloration unit is connected by condenser 16 with the liquefied ammonia surge tank 17.Through decoloration unit
Ammonia is condensed through condenser 16, obtains the liquefied ammonia product of high quality.
Optionally, described device include at least two decoloration units, first decoloration unit 14 and second decoloration unit 15, two
It is arranged in parallel between a decoloration unit, one opens one standby, can switch regeneration in time.
Referring to FIG. 2, its structural schematic diagram for decoloration unit provided in an embodiment of the present invention.The decoloration unit includes
Shell 141, shell 141 is interior to form circulation chamber and transition chamber 143 by the isolation of activated carbon fiber layers 142, and the circulation chamber is by baffle
144 isolation form feed space 145 and discharge chamber 146；The feed space 145 is connected with the rectifying column 13, the discharge chamber 146
It is connected with the liquefied ammonia surge tank 17.Using the decoloration unit of the structure setting, ammonia is in decoloration unit, with activated carbon fibre
Layer 142 is capable of the impurity such as the organic matter of the contact removing adsorption of cross-flow twice, obtains the liquefied ammonia product of high quality.
The feed end of the decoloration unit is provided with ammonia entrance 1451；It is additionally provided with regeneration steam outlet 1462.Institute
The discharge end for stating decoloration unit is provided with ammonia outlet 1461；It is additionally provided with regeneration steam entry 1452.Each outlet setting
There is valve for regulating and controlling open and-shut mode and flow etc..
Optionally, the shell 141 of the decoloration unit can be the global shell, square shell, cylindrical shell etc. of rule,
It can be other irregular shells.
Optionally, the activated carbon fiber layers 142 in decoloration unit can be an independent activated carbon fiber layers, be enclosed stream
Logical room；Decoloration unit is also possible to more than one activated carbon fiber layers, is connected to each other and is enclosed circulation chamber.
The present invention also provides a kind of methods of liquefied ammonia refinery decolorization, include the following steps:
Thick ammonia obtains liquefied ammonia through preliminary purification processing, purification, fractional condensation water removal, desulfurization process, rectifying, decoloration.
Specifically, thick ammonia removes most water, organic impurities and solid impurity through the first clean unit 1, then from ammonia
3 bottom of treater enters, and comes into full contact with the concentrated ammonia liquor adverse current of circulation, and following reaction NH occurs3·H2O+H2S→NH4HS+H2O,
2NH3·H2O+H2S→(NH4)2S+2H2O, the condition in ammonia gas finisher are as follows: 0 DEG C~10 DEG C, 0.15MPa~0.25MPa, wherein
Most H2S is washed to be absorbed into the concentrated ammonia liquor of circulation, realizes the preliminary removing H of thick ammonia2S；Preliminary removing H2The ammonia of S
It imports segregator 5 to condense with the liquefied ammonia hybrid cooling from liquefied ammonia surge tank 17, controlling the temperature in segregator is 0 DEG C~10
DEG C, the moisture carried secretly from ammonia gas finisher 3 is isolated, the ammonia after fractional condensation imports in crystallizer 6, and temperature is -10 in crystallizer
DEG C~0 DEG C, by low temperature desublimation by NH4HS and (NH4)2S is crystallized on multilayer crystallization plates, realizes the further net of ammonia
Change.Then the fine de-sulfur device 8, H for having fine desulfurization catalyst is imported after preheated device 7 preheats2Other materials are generated after S reaction to stop
It stays in catalyst bed, realizes the further purification of ammonia, guarantee hydrogen sulfide content≤10ppm.Fine de-sulfur treated ammonia
Gas enters ammonium hydroxide preparing tank 9, with the weak aqua ammonia mixed preparing concentrated ammonia liquor from 13 bottom of rectifying column, through First Heat Exchanger 10, delays
The temperature for rushing concentrated ammonia liquor after tank 11 and the second heat exchanger 12 reaches 100 DEG C~115 DEG C, is subsequently poured into rectifying column 13, rectifying column
Pressure 1.4MPa~1.5MPa, tower top temperature are 45 DEG C~55 DEG C, and column bottom temperature is 140 DEG C~150 DEG C, highly concentrated derived from tower top
It spends ammonia and enters the first decoloration unit 14, ammonia enters feed space 145 from the ammonia entrance 1451 of decoloration unit bottom, with activity
Then organic impurities in the cross-flow twice of Carbon fibe layer 142 contact removing ammonia collects such as phenols and light oil and enters going out for top
Expect room 146, be discharged through ammonia outlet 1461, the high concentration ammonia of discharge is condensed through condenser 16, and the liquefied ammonia for obtaining high quality produces
Product are stored in liquefied ammonia surge tank 17.
Wherein, clean unit and decoloration unit are two settable, and one opens one standby, can switch regeneration in time.Regenerative process
It is carried out using 0.78MPa, 169 DEG C of vapor.By taking the first decoloration unit 14 as an example, when regeneration, vapor is from decoloration unit top
The regeneration steam entry 1452 in portion enters discharge chamber 146, contacts removing surface by two sides cross-flow with activated carbon fiber layers 142
The organic impurities of absorption, the feed space 145 that mixer collects into bottom are regenerated at the discharge of steam outlet 1462
Reason.
Embodiment 1
The present embodiment is the specific method that liquefied ammonia refinery decolorization is carried out using above-mentioned apparatus, is included the following steps:
(1) thick ammonia removes most water, organic impurities and solid impurity through the first clean unit 1；
(2) ammonia through step (1) purified treatment enters from 3 bottom of ammonia gas finisher, abundant with the concentrated ammonia liquor adverse current of circulation
It contacts, the condition in ammonia gas finisher are as follows: 0 DEG C~10 DEG C, 0.15MPa~0.25MPa, following reaction NH occurs3·H2O+H2S→
NH4HS+H2O, 2NH3·H2O+H2S→(NH4)2S+2H2O, the H of wherein most2S is washed to be absorbed into the concentrated ammonia liquor of circulation,
Realize the preliminary removing H of thick ammonia2S；
(3) segregator 5 will be imported through the ammonia of preliminary purification in step (2) to mix with the liquefied ammonia from liquefied ammonia surge tank 17
Cooling condensation, controlling the temperature in segregator is 0 DEG C~10 DEG C, isolates the moisture carried secretly from ammonia gas finisher 3；
(4) it will be imported in crystallizer 6 through the ammonia of fractional condensation processing in step (3), temperature is -10 DEG C~0 DEG C in crystallizer,
By low temperature desublimation by NH4HS and (NH4)2S is crystallized on multilayer crystallization plates, realizes the further purification of ammonia；
It (5) will treated imports after the preheated device 7 of ammonia preheats and have fine desulfurization catalyst for crystallization sulphur removal in step (4)
Fine de-sulfur device 8, H2Other materials are generated after S reaction to rest in catalyst bed, realize the further purification of ammonia, are guaranteed
Hydrogen sulfide content≤10ppm；
(6) treated the ammonia of fine de-sulfur in step (5) is sent into ammonium hydroxide preparing tank, and from the dilute of 13 bottom of rectifying column
Ammonium hydroxide mixed preparing concentrated ammonia liquor, the temperature of concentrated ammonia liquor reaches 100 after First Heat Exchanger 10, surge tank 11 and the second heat exchanger 12
DEG C~115 DEG C, it is then fed into rectifying column 13, Rectification column pressure 1.4MPa~1.5MPa, tower top temperature is 45 DEG C~55 DEG C, tower
Bottom temperature is 140 DEG C~150 DEG C；
Wherein, the weak aqua ammonia of tower bottom is sent into ammonium hydroxide preparing tank 9 according in step (6)；
(7) derived from the tower top of rectifying column 13 high concentration ammonia enter first decoloration unit 14, ammonia from decoloration unit
The ammonia entrance 1451 of bottom enters feed space 145, contacts with the cross-flow twice of activated carbon fiber layers 142 organic in removing ammonia
Then impurity collects the discharge chamber 146 for entering top, is discharged through ammonia outlet 1461, the high concentration ammonia of discharge is through condenser
16 condensations, the liquefied ammonia product for obtaining high quality are stored in liquefied ammonia surge tank 17.
Obtained liquefied ammonia product is detected, ammonia content is greater than 99.9%, and water content is less than 0.1%, hydrogen sulfide 1ppm,
Phenols 3ppm.
Embodiment 2
The liquefied ammonia refinery decolorization method of the present embodiment reference implementation example 1, difference are only that: by the step (7) in embodiment 1
In decoloration unit replace with common activated carbon adsorption unit, other operating conditions and embodiment 1 are consistent, and the liquefied ammonia of preparation produces
Product data are as follows: ammonia content is greater than 99.8%, and water content is less than 0.1%, hydrogen sulfide 1ppm, phenols 9.5ppm.
Comparative example 1
The liquefied ammonia process for refining of comparative example 1, not comprising the step (1) and step (7) in embodiment 1, other operating conditions
Consistent with embodiment 1, the liquefied ammonia product data of preparation are as follows: ammonia content is greater than 99.8%, and water content is less than 0.2%, hydrogen sulfide
1ppm, phenols 10ppm.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of device of liquefied ammonia refinery decolorization, which is characterized in that including sequentially connected clean unit, ammonia gas finisher, fractional condensation
Device, crystallizer, preheater, fine de-sulfur device, ammonium hydroxide preparing tank, rectifying column, decoloration unit and liquefied ammonia surge tank；
The liquefied ammonia surge tank is also connected with the segregator；
The discharge end of the ammonium hydroxide preparing tank is connected by heat exchanger with the feed end of the rectifying column；
The ammonia gas finisher is for contacting thick ammonia with concentrated ammonia liquor to remove H2S；
Contain desulphurization catalyst in the fine de-sulfur device.
2. the device of liquefied ammonia refinery decolorization according to claim 1, which is characterized in that the decoloration unit includes shell,
It is isolated in the shell by activated carbon fiber layers and forms circulation chamber and transition chamber, the circulation chamber is isolated by baffle forms feed space
And discharge chamber；The feed space is connected with the rectifying column, and the discharge chamber is connected with the liquefied ammonia surge tank；
Optionally, described device includes at least two decoloration units, is arranged in parallel between each decoloration unit；
Optionally, the feed end of the decoloration unit is provided with ammonia entrance；
Optionally, the discharge end of the decoloration unit is provided with ammonia outlet；
Optionally, the feed end of the decoloration unit is provided with regeneration steam outlet；
Optionally, the discharge end of the decoloration unit is provided with regeneration steam entry.
3. the device of liquefied ammonia refinery decolorization according to claim 1 or 2, which is characterized in that the bottom of the rectifying column goes out
Material end is connected with the feed end of the ammonium hydroxide preparing tank；
Optionally, the bottom discharge end of the rectifying column is connected by heat exchanger with the feed end of the ammonium hydroxide preparing tank.
4. the device of liquefied ammonia refinery decolorization according to claim 1 or 2, which is characterized in that the ammonia gas finisher is circumscribed with
Ammonia circulation pump；
Optionally, the top feed that the bottom discharge end of the ammonia gas finisher passes through ammonia circulation pump and the ammonia gas finisher
End is connected.
5. the device of liquefied ammonia refinery decolorization according to claim 1 or 2, which is characterized in that the clean unit with it is described
The bottom feed end of ammonia gas finisher is connected.
6. the device of liquefied ammonia refinery decolorization according to claim 1 or 2, which is characterized in that the liquefied ammonia surge tank and institute
Ammonia gas finisher is stated to be connected.
7. the device of liquefied ammonia refinery decolorization according to claim 1 or 2, which is characterized in that the ammonium hydroxide preparing tank goes out
Material end is connected by heat exchanger, surge tank with the feed end of the rectifying column.
8. a kind of method of liquefied ammonia refinery decolorization, which comprises the steps of:
Slightly ammonia handles through preliminary purification, removes water with concentrated ammonia liquor contact treating, fractional condensation, crystallize desulfurization and fine de-sulfur processing, rectifying, take off
Color obtains liquefied ammonia.
9. the method for liquefied ammonia refinery decolorization according to claim 8, which is characterized in that the condition of the purification includes: in 0
DEG C~10 DEG C, 0.15MPa~0.25Mpa, with concentrated ammonia liquor haptoreaction；
Optionally, the preliminary purification processing is carried out using active carbon；
Optionally, the temperature of the fractional condensation water removal is 0 DEG C~10 DEG C.
10. the method for liquefied ammonia refinery decolorization according to claim 8, which is characterized in that the method packet of the crystallization desulfurization
It includes: in -10 DEG C~0 DEG C progress crystallization treatment；
Optionally, it is 45 DEG C~55 DEG C that the condition of the rectifying, which includes: tower top temperature, and column bottom temperature is 140 DEG C~150 DEG C, pressure
Power is 1.4MPa~1.5MPa；
Optionally, decolorization is carried out using activated carbon adsorption fiber.
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| CN112275262A (en) * | 2020-11-16 | 2021-01-29 | 中国石油化工股份有限公司 | Refinery anhydrous liquid ammonia decolorant and preparation method thereof |
| CN112717634A (en) * | 2020-11-28 | 2021-04-30 | 安徽金禾实业股份有限公司 | Filtering and decoloring device and method for ammonia water |
| CN113104861A (en) * | 2021-05-10 | 2021-07-13 | 中国科学院过程工程研究所 | System and method for recycling ammonia in coal chemical industry wastewater containing complex color development impurities |
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| CN205387479U (en) * | 2015-12-24 | 2016-07-20 | 宁波中金石化有限公司 | Sour water strip ammonia purification liquid ammonia decoloration device |
| CN106395857A (en) * | 2016-08-29 | 2017-02-15 | 北方华锦化学工业集团有限公司 | Liquid ammonia refining decolorization system and method |
| CN109399666A (en) * | 2018-12-14 | 2019-03-01 | 南京新世纪江南环保科技发展有限公司 | A kind of method and device recycling ammonia from acid water |
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| CN1587045A (en) * | 2004-08-16 | 2005-03-02 | 中国石油化工集团公司 | Ammonia refining combined process |
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| CN112275262A (en) * | 2020-11-16 | 2021-01-29 | 中国石油化工股份有限公司 | Refinery anhydrous liquid ammonia decolorant and preparation method thereof |
| CN112717634A (en) * | 2020-11-28 | 2021-04-30 | 安徽金禾实业股份有限公司 | Filtering and decoloring device and method for ammonia water |
| CN113104861A (en) * | 2021-05-10 | 2021-07-13 | 中国科学院过程工程研究所 | System and method for recycling ammonia in coal chemical industry wastewater containing complex color development impurities |
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| CN110395746B (en) | 2021-06-04 |
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