# Patent

## Title
Urea granulation process with scrubbing system

## Abstract

A urea granulation process with a scrubbing system may involve at least one gaseous waste stream for removal of dust and ammonia whereby the waste stream may be processed through a combination of process steps. In some examples, the process steps may involve washing the dust and ammonia laden stream with water and/or an aqueous urea solution whereby a dust-laden liquid stream and a dust-reduced stream is generated. The process steps may further involve reacting the dust-reduced stream with formaldehyde to form a stream comprising hexamethylenetetramine and urea-formaldehyde and clean off-gas. In some cases, the gas stream may be directed first through the washing step and then through the reacting step.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a divisional application of U.S. patent application Ser. No. 14/399,473 filed on Nov. 6, 2014, which is a U.S. National Stage Entry of International Patent Application No. PCT/EP2013/001292 filed May 2, 2013, which in turn claims priority to European Patent Application No. 12003585.2 filed May 8, 2012, all of which are incorporated herein by reference in their entireties.


FIELD
The present disclosure generally relates to a urea granulation process and to the apparatus suitable for operating such a process. The present disclosure integrates a method for reducing ammonia emissions from a urea granulation plant that is currently emitted by a conventional urea production process by scrubbing the off-gas. Several advantages of the scrubbing system concern reducing an amount of ammonia in off-gas and reducing the generation of ammonium salts.
BACKGROUND
A common process for producing granules from a liquid composition is described in U.S. Pat. No. 5,779,945. The focus of U.S. Pat. No. 5,779,945 is the treatment and sorting of generated granules with different sizes. Herein a gas/solids separating apparatus such as a cyclone or a scrubber is used to separate solid material from the off-gas stream of the apparatus. Advanced treatment of the off-gas stream is not taken into further account.
In U.S. Pat. No. 4,370,198 the off-gas of the granulation unit is sent to a dust separation cyclone followed by a continuous wet scrubber which both contributes to the scrubbing off said off-gas stream. The scrubbing liquid used is part of the solution or suspension to be proceeded and the scrubbing liquid leaving the wet scrubber is fed back directly into the granulation unit. Exemplarily, the described process can be achieved for the production of sodium chloride, urea, saccharose or ferric oxide, respectively. Hereby the scrubbing liquor is part of the solution or suspension to be processed and is send directly back into the granulation unit. This process can be only achieved for dust scrubbing but is not suitable for ammonia scrubbing.
A further example for an apparatus and a method for wet type simultaneous cleaning and dust-removing gas treatment in a horizontal cross-flow scrubber are disclosed in EP 0853971 A1. The present disclosure performs the removal of pollutants and dust in a packed tower.
In a urea plant used air exiting a urea granulator that is equipped with a fluidized bed contains in addition to urea dust also ammonia. This ammonia contamination needs to be removed before the off-gas stream can be vented into the atmosphere.
Removing ammonia from an off-gas stream is a well-known technology. Usually the off-gas stream is treated with an acidic scrubbing solution. This scrubbing solution can be easily manufactured by adding an acid such as nitric acid or sulphuric acid to water. The ammonia is removed from the gas stream by chemical absorption and converted to the corresponding ammonium salt. The use of nitric acid produces ammonium nitrate (AN), and the use of sulphuric acid produces ammonium sulphate (AS) respectively. These ammonium salt-containing solutions can be used for the production of ammonium sulphate fertilizer or NPK fertilizer, the technology for this is state of the art.
In a urea plant, ammonium salts do not occur in the process and cannot easily be processed at existing urea facilities. A conventional urea production facility therefore has only the following options to reduce gaseous ammonia emissions from the granulation plant:

    
    
        to discharge the diluted ammonium salt solution to a waste water stream,
        to concentrate the diluted ammonium salt solution up to a concentration which can be utilized by other plants, e.g. NPK,
        to produce UAS (urea/ammonium sulphate) fertilizer with a high sulphur content,
        to produce UAN (urea/ammonium nitrate) solution.

All of these alternatives require significant investments and changes to operating conditions or entail changes of the product composition and characteristics. All above options result in new products that require additional facilities for transport and handling as well as energy utilities in expensive quantities. As a consequence, nowadays, urea facilities are run without efficient ammonia removal causing severe environmental problems. Therefore, ammonia removal from a urea facility is a challenging task that needs to be solved.

    
    


An alternative solution is described in WO 03/099721. The present disclosure relates to a process for removing ammonia from an ammonia-containing gas stream by converting the ammonia in the ammonia-containing gas stream with an organic acid into an ammonium salt, whereas the obtained ammonium salt is contacted, at elevated temperature, with peroxide. The ammonium salt is hereby converted into a NH3, CO2 and H2O containing mixture in a decomposer and can readily be reprocessed in a urea synthesis unit. The peroxide is supplementary to the common process and may relate to other negative accompaniments. Also, for the conversion of the ammonium salt into NH3, CO2 and H2O a separate decomposer in addition to the normal plant layout is required. This emerging gas stream can not be reprocessed in a granulation unit but needs to be recycled in a urea synthesis unit.
Reductions of ammonia emissions are also described in M Potthoff, Nitrogen+Syngas, [online], July. August 2008, pages 39-41. In FIG. 1 a combined dust and acidic scrubber system is shown. The ammonia is absorbed in the acidic scrubbing section and converted into ammonium sulphate. The ammonium sulphate solution is added to the recycle flow going back to the evaporation section. In this unit it is mixed with urea melt from the urea synthesis unit. The concentrated liquor stream from the evaporation is conveyed into the urea granulator. The condensate coming out of the evaporation unit is utilised as makeup for the combined dust/ammonia scrubbing system. With this so called Ammonia Convert Technology ammonia in off-gas can be reduced to 30 mg/Nm3. The technology without acidic scrubbing as shown in Brochure Urea, [online], 12-2007, pages 1-24 reduces ammonia in off-gas only to values of around 160 mg/m3.
The ammonia convert technology described in M Potthoff, Nitrogen+Syngas, [online], July. August 2008, pages 39-41 implicates still several disadvantages. First of all, the water balance in this system is a critical parameter. If disturbed, urea synthesis will be contaminated with ammonium sulphate or alternatively large amounts of waste water need to be treated. In addition, mixing of acidic solution with concentrated urea melt in the evaporation unit has adverse effects on granulation. Moreover, this technology implicates the generation of large amounts of condensate contaminated with ammonium sulphate that needs to be distributed to various scrubbers, including dust and acidic scrubbing technology. Also the remaining ammonia concentration in the off-gas achieved with this technology is still not sufficient or satisfactory for modern urea granulation plants.
In WO 2010/060535 A1 the ammonia convert technology described in M Potthoff, Nitrogen+Syngas, [online], July. August 2008, pages 39-41 is improved in order to achieve ammonia concentrations in off-gas of 10 mg/Nm3. WO 2010/060535 A1 teaches that a scrubber dust stage, that is connected to process coolers, is operated through an ammonium salt solution stream generated in a scrubber acid stage, which is connected to the urea granulator. Therefore the scrubbing system presented in WO 2010/060535 A1 represents an in itself complete closed system as described in the characteristic part of claim 1 of the present disclosure. This technology avoids contamination of the urea melt generated in the urea synthesis unit by building such a complete closed scrubbing system. The disadvantage of this system is that it is very complex in its performance.
In U.S. Pat. No. 5,686,647 a process for preparing urea is described wherein an amount of formaldehyde is added to an off-gas stream containing gaseous ammonia to form hexamethylenetetramine, which is returned into the process before the granulation step. This formaldehyde addition can be performed before or during a washing step with liquid urea solution whereby this washing step serves as dust scrubbing device. The disadvantage of this technology is the relatively high amount of ammonia in the off-gas of circa 90 mg/Nm3 in comparison to the technology presented in WO 2010/060535 A1.



BRIEF DESCRIPTION OF THE DRAWINGS
The present disclosure is described in detail below with reference to the attached drawing figures.
FIG. 1 is a schematic block diagram of an embodiment of a urea granulation process utilizing an ammonia formaldehyde convert process, as disclosed herein.
FIG. 2 is a schematic block diagram of an embodiment of a urea granulation process utilizing an ammonia formaldehyde convert process, including a scrubber acid stage, as disclosed herein.
FIG. 3 is a schematic block diagram of an embodiment of a urea granulation process including a closed scrubbing system, as disclosed herein.



DETAILED DESCRIPTION
An object of the present disclosure is to provide a process that integrates and optimizes technology for scrubbing off-gas generated by a urea granulation process. The process eliminates problems associated with the use of conventional technologies as described above, and should be easy to integrate into current state of the art scrubbing systems. It is also an object of the present disclosure to provide an apparatus suitable to perform such a process.
This object and other objects are achieved by a urea granulation process with scrubbing system including at least one gaseous waste stream for removal of dust and ammonia whereby this waste stream is processed through a combination of the following process steps comprising

    
    
        (a) washing the dust and ammonia laden stream 4 with water and/or an aqueous urea solution whereby a dust-laden liquid stream 26 and a dust-reduced stream 5 is generated, and
        (b) reacting the dust-reduced stream 5 with formaldehyde 7 to form a stream comprising hexamethylenetetramine and urea-formaldehyde 8 and clean off-gas 6
        wherein the gas stream is directed first through process step (a) and then through process step (b).
    
    


Surprisingly the sequence of process steps in the above disclosed embodiment of a method of the present disclosure permits further reduction of ammonia emissions from granulation plants in comparison to the technology described in U.S. Pat. No. 5,686,647, in which the order of process steps is reversed. If process step (b) is done before the dust scrubbing in process step (a) the reaction ammonia-formaldehyde suffers from competition with the standard urea-formaldehyde reaction which would prevail in the dilute urea solution obtained in the scrubber. Therefore efficiency in this process step is lost and ammonia-reduction is limited.
Hereby the urea concentration of the dust-laden liquid stream 26 is kept in a range from 35 to 60% wt, and preferably is kept in a range from 45 to 55 wt and that dust laden liquid stream 26 is returned into the process before the granulation step.
Furthermore 70 to 90 wt % of ammonia in relation to the total ammonia content of the dust-reduced stream 5 is reacted to hexamethylenetetramine in the formaldehyde stage 2.
Optionally, the stream comprising hexamethylenetetramine and urea-formaldehyde 8 is returned into the process before the granulation step. The hexamethylenetetramine comprises urea-formaldehyde solution and therefore replaces at least part of the urea/formaldehyde solution normally used as granulation additive.
In a further embodiment of the current process the dust-laden liquid stream 26 is mixed with the stream comprising hexamethylenetetramine and urea-formaldehyde 8 before returning this mixture into the process before the granulation step.
In a further embodiment of the present disclosure an additional process step for removing ammonia is implemented downstream of process step (b) wherein an ammonia-laden stream is brought into contact with an acid 9 in liquid phase and thereby ammonia is scrubbed from that stream by the generation of an ammonium salt stream 10 in a scrubber acid stage 3.
The combination of these three process steps bears the advantage that the amount of ammonium salt generated in the scrubber acid stage 3 is greatly reduced so that these salts do not disturb the granulation system or the urea synthesis system if recycled back in one of these systems. Also the amount of ammonia reduced by this system can be improved.
Hereby 94 to 99.9% of ammonia in relation to the total ammonia content of the dust- and ammonia-laden stream 4 is eliminated through the combination of process steps (a) and (b) with a further acidic treatment.
In an embodiment of the present disclosure the acid is selected from the group consisting of sulphuric acid, nitric acid, phosphoric acid, citric acid, lactic acid and oxalic acid. Other acids can be used if they are non-volatile. Preferably, sulphuric acid is used, as it is readily available and in addition, it supplies sulphur which is considered to be a highly demanded nutrient.
Furthermore the ammonia salt concentration of the ammonium salt stream generated in the scrubber acid stage is kept <40% wt, and preferably is kept in a range from 35-40% wt.
The pH of the ammonia salt stream generated in the granulator scrubber acid stage is kept in a range from 2-6, and preferably is kept in a range from 3.5-5.0, and most preferably is kept in a range from 4.0-4.5.
In an optional embodiment a second gaseous dust- and ammonia-laden stream 14 drawn off from product coolers 13 is generated, which stream is send through a further scrubber dust stage 15 in which the ammonium salt stream 10 of the further acid treatment is used to remove the ammonia from this second gaseous dust- and ammonia-ladden stream 14.
In a further optional embodiment of the present disclosure the scrubbing system being passed is in itself a complete closed system, whereby

    
    
        the ammonium salt stream 10 from the scrubber acid stage 3 is fed into said further scrubber dust stage 15, and
        the released solution 17 from said further scrubber dust stage 15 is send to a evaporation unit 16,
        the vapour stream 18 from the evaporation unit 16, which contains ammonia is given into a condenser unit 19, which releases a liquid process condensate 20, and said liquid process condensate 20 is given into the scrubber acid stage 3, and
        the concentrated liquor stream 21 generated in the evaporation unit 16, containing urea and ammonium salt, and a urea melt 22 is conveyed into the urea granulator 1.
    
    


Hereby the scrubbing system in itself is a complete closed system, and is therefore totally decoupled from urea synthesis. Thereby contaminations of the urea melt are totally avoided.
With advantage the concentration of the urea melt 22 and concentrated liquor stream 21, containing urea and ammonium salt, for the urea granulator being kept in a range from 95 to 99.8% wt, and being preferably kept in a range from 96 to 97.5% wt.
Optionally a portion of urea melt 22 is fed into the evaporation unit 16.
Furthermore the clean off-gas 6 is released into the atmosphere and exhibits a concentration of NH3 in the range of 5-30 mg/Nm3, and preferably exhibits a concentration of NH3 being <10 mg/Nm3.
The present disclosure also comprises an apparatus with scrubbing system system including at least one gaseous waste stream for the removal of dust and ammonia comprising

    
    
        a scrubber dust stage 11, in which dust is washed off from a dust- and ammonia-ladden stream, and
        a formaldehyde stage 2, in which part of the ammonia of the ammonia-ladden air 4 is reacted with formaldehyde 7 to form hexamethylenetetramine,
    
    


whereby the scrubber dust stage 11 is arranged upstream of the formaldehyde stage 2.
Furthermore an additional scrubber acid stage 3 is integrated into the scrubbing system downstream of the formaldehyde stage 2.
Optionally the urea granulation apparatus with scrubbing system comprises also product coolers 13, in which a second gaseous ammonia-laden stream 14 is generated, and which product coolers 13 are connected with a further scrubber dust stage 15 which is connected with means for conveying the ammonium salt solution stream 10 from the scrubber acid stage 3 to said further scrubber dust stage 15.
In a further embodiment of the urea granulation apparatus the apparatuses of the scrubbing system being connected in such a way that a complete closed system of waste streams is built, comprising

    
    
        means for conveying the ammonium salt stream 10 from the scrubber acid stage 3 to the further scrubber dust stage 10, and
        means for conveying the solution 17 from said further scrubber dust stage 15 to an evaporation unit 16,
        means for conveying the steam vapour 18 of the evaporation unit 16 to a condenser unit 19,
        means for conveying the process condensate 20 from the condenser unit 19 to the granulator scrubber acid stage 3, and
        means for conveying urea melt 22 and a means for conveying a concentrated liquor stream 21, containing urea and ammonium salt into the urea granulator 1.
    
    


Furthermore the apparatus comprises means for conveying a portion of urea melt to the evaporation unit 16.
With advantage scrubbers used in the current technology are horizontal scrubbers.
With reference now to the figures, FIG. 1 shows an urea granulator 1, which is supplied with urea melt or an aqueous urea solution 22. In the urea granulator 1 urea granules are formed in a fluidized bed, which is fluidized by an air stream 27. A dust- and ammonia-laden stream 4 is drawn off. It is first scrubbed in the scrubber dust stage 11, where urea dust is removed. A stream of process water or diluted urea solution 12 is added to the scrubber dust stage 11 and the dust-laden stream 26 is drawn-off from the scrubber dust stage 11. The dust-reduced stream 5 is then sent to the formaldehyde stage 2. According to the present disclosure formaldehyde 7 is introduced in the formaldehyde stage 2. A hexamethylenetetramine and formaldehyde containing stream 8 is drawn-off from the formaldehyde stage 2. This hexamethylenetetramine can be returned into the granulation process before the granulation step. The clean off-gas 6 is send into the atmosphere.
FIG. 2 includes in comparison to FIG. 1 an additional scrubber acid stage 3 downstream of the formaldehyde stage 2. The ammonia reduced stream 29 from the formaldehyde stage 2 is send into the scrubber acid stage 3 where the rest of ammonia is removed, and the clean off-gas stream 6 can be drawn off. The scrubbing solution for the scrubber acid stage 3 consists of process water and the acid 9 in liquid phase. In the granulator scrubber acid stage 3 the acid solution reacts with ammonia producing an ammonium salt stream 10. This ammonium salt stream 10 can be further processed as shown in FIG. 3 or can be drawn-off from the urea granulation system.
This inventive process allows the reduction of ammonium salts generated in the scrubber acid stage 3 but is very effective in reducing ammonia emissions from urea granulation plants. Ammonium salts are much undesired because they cause severe environmental problems and cause problems in urea granule quality if added to high concentrations to the granulation process.
FIG. 3 includes in comparison to FIG. 2 a in itself closed scrubbing system including the inventive process steps. In addition to FIG. 2 product coolers 13 are shown, in which the hot granules 25 produced are conveyed. Air 28 cools the final product 25. The dust-laden air stream 14 is conveyed to a further scrubber dust stage 15, where the urea dust is washed out while the air is cooled down by evaporation of water in the scrubber. The clean off-gas 23 leaving the scrubber dust stage 15 is to the atmosphere.
The resulting solution 17 from the scrubber dust stage 15, is combined with the dust-laden stream 26 from the granulator scrubber dust stage 11 and the resulting mixture is conveyed to the evaporation unit 16, where it is concentrated. The concentrated liquor stream 21 from the evaporation unit 16 is fed to the urea granulator 1 to integrate the generated ammonium salt into the granulation process. A portion of the urea melt 22 can be added to the evaporation unit 16 (not shown), in order to keep the urea concentration and the ammonium sulphate concentration of the concentrated liquor stream 21 in the right ratio. The steam vapour 18 drawn off from the evaporation unit 16 is conveyed to a condenser unit 19, where it is cooled by external cooling water. The liquid process condensate 20 generated during the condensation is send into the scrubber acid stage 3. To close the scrubbing cycle the ammonium salt stream 10 drawn-off from the scrubber acid stage 3 is send to the scrubber dust stage 15.
Therefore a closed circle of waste streams is formed and all waste streams are recycled. In addition the generated ammonium salts are integrated in the urea granulation process. Also external process water consumption is reduced to a minimum. Altogether, this combination is characterized by its environmental compatibility. Also the content of ammonium salt in the generated urea granules is reduced, which gets problematic if sulphuric acid is used as acid 9 and the sulphur content of the granules increase.
Example 1
In example 1 a table is shown giving some typical figures concerning ammonia in the urea granulation processes state of the art as described in Brochure Uhde, Urea, [online] 2011 compared with a formaldehyde treatment as described in U.S. Pat. No. 5,686,647 implemented before or combined with a scrubber dust stage and the inventive technology.
In a urea granulation process with formaldehyde scrubbing a formaldehyde-containing solution is added to the ammonia-laden air or the formaldehyde stage.
The formaldehyde-containing solution used for scrubbing is charged with hexamethylenetetramine and is partially reintroduced into the above described urea process. Basically this mixture after being brought to the right pressure and temperature may be recycled in every phase of the process.
The amount of ammonia of 500 to 600 ppm by weight in the feed to the granulation unit is more or less unavoidable as it is the result of the equilibrium formed in an upstream to the granulation unit arranged evaporation unit, if the concentrated liquor stream generated in this evaporation unit shall be introduced into the granulator. About 90 ppm ammonia is added through biuret formation in the urea solution, which is fed into the granulator, so that in total about 590 to 690 ppm enters the granulation unit.
About 50 ppm of this ammonia is included in the final product, whereby the rest leaves the granulation plant with the air flow from the granulation unit via stacks. This results in a final concentration of approximately 130 to 160 mg/Nm3 for the technology state of the art as presented in Brochure Urea, [online], 2011. In the technology described by U.S. Pat. No. 5,686,647 a final concentration of circa 86 mg/Nm3 can be reached. If formaldehyde stage is put into practice after a dust scrubber where the urea is almost removed, as the present disclosure shown in FIG. 1 suggests, a final concentration of approximately 30 mg/Nm3 ammonia is found in a combined stack. The inventive technology in combination with a following acid scrubbing stage as shown in FIG. 2 can lead to ammonia concentrations of 10 mg/Nm3 with a minor amount of acid to be used. Therefore a drastically improvement can be achieved using this technology.







TABLE 1







technology state of the art in comparison with present disclosure













formaldehyde treat-
formaldehyde treat-
Formaldehyde treat-



technology state
ment as described in
ment of the present
ment of the present



of the art
U.S. Pat. No. 5,686,647
disclosure as shown
disclosure as shown



(Brochure Urea, 2011)
before a scrubber dust stage
in FIG. 1
in FIG. 2












Free ammonia from
□ 500 to 600 ppm wt.


evaporation unit


Ammonia from
□ 90 ppm wt.


biuret formation


Total free ammonia
□ 590 to 690 ppm wt.


at granulator inlet


Free ammonia in
□ 50 ppm wt.


final product


Free ammonia
□ 540 to 640 ppm wt.


released (based on


urea solution)











Ammonia -
none
yes
yes
yes


formaldhyde stage


Dose Formaldehyde

4
4
4


as UFC via


7 kg/ton


Typical ammonia
□ 130 to 160
□ 86
□ 30
□ 10


concentration in
mg/Nm3
mg/Nm3
mg/Nm3
mg/Nm3


combined stack
□ 0.6 to 0.7
□ 0.40
□ 0.14
□ 0.05



kg/tonproduct
kg/tonproduct
kg/tonproduct
kg/tonproduct


Formaldehyde

45.00%
75.00%
75.00%


efficiency


Ammonium



≅0.35


sulphate produced



kg/tonproduct









The efficiency of formaldehyde to abate ammonia is strongly reduced to only 45% if the process is done before the dust scrubbing. If it is done in combination with the dust scrubbing the formaldehyde efficiency is 75%. The reaction ammonia-formaldehyde suffers from competition with the standard urea-formaldehyde reaction which would prevail in the dilute urea solution obtained in the scrubber. Therefore the change in the sequence of process steps of the present disclosure in relation to the teaching of U.S. Pat. No. 5,686,647 has an enormous positive effect in respect to the ammonia content in off-gas. The combination shown in FIG. 2 of a scrubber acid stage downstream of the formaldehyde stage has the advantage that the ammonium salt stream generated has a very low ammonium salt concentration if compared with the technology state of the art of WO2010060535A1 (table 2) in which a formaldehyde stage is missing. Therefore this ammonium salt stream can be exported from the granulation system or can be further processed as shown in FIG. 3.
Example 2
In example 2 a table is shown giving some typical figures concerning ammonia in the urea granulation processes state of the art as described in WO2010060535A1, in which the ammonium salt stream generated is reintroduced into the granulation process, whereby a in itself complete closed system of scrubbing streams is built, compared with the inventive closed scrubber technology as shown in FIG. 3.
In a urea granulation process with a scrubber system according to FIG. 3 a formaldehyde-containing solution is added via 7 to the formaldehyde stage 2.
The formaldehyde-containing solution used for scrubbing in formaldehyde stage 2 is charged with hexamethylenetetramine and is partially reintroduced into the standard urea process. Basically this mixture after being brought to the right pressure and temperature may be recycled in every phase of the process.







TABLE 2







technology state of the art in comparison


with present disclosure as shown in FIG. 3:











technology state
Ammonia convert
Inventive



of the art
technology
technology



(Brochure Urea, 2011)
WO2010060535A1
(FIG. 3)












Free ammonia from
□ 500 to 600 ppm wt.


evaporation section


Ammonia from
□ 90 ppm wt.


biuret formation


Total free ammonia
□ 590 to 690 ppm wt.


at granulator inlet


Free ammonia in
□ 50 ppm wt.


final product


Free ammonia
□ 540 to 640 ppm wt.


released (based on


urea solution)










Ammonia -
none
none
yes


formaldhyde stage


Dose Formaldehyde


4


as UFC via


7 kg/ton


Formaldehyde


75.00%


efficiency


Acid scrubber
none
yes
yes


stage


Typical ammonia
≈130 to 160
≈10
≈10


concentration in
mg/Nm3
mg/Nm3
mg/Nm3


combined stack
≅0.6 to 0.7
≅0.05
≅0.05



kg/tonproduct
kg/tonproduct
kg/tonproduct


Sulphuric acid

≅2.0
≅0.27


consumption

kg/tonproduct
kg/tonproduct


Ammonium sulphate

≅2.3
≅0.35


produced

kg/tonproduct
kg/tonproduct









Thus, a solution is produced which shows ammonia concentrations in off-gas that are comparable to those reached with the technology described in WO2010060535A1. But in addition a very low ammonium salt concentration, which is approx. 8 times less then the technology described in WO2010060535A1 is produced. Also the sulphuric acid consumption is 8 times lower which is a significant cost reduction. There is no significant change to the product specification and quality by the addition of these small amounts of ammonium salts. The N content of the urea product stays above 46% N, so that the product is still a typical urea fertilizer.
Some example advantages of the proposed process include the following:

    
    
        significant low ammonia emissions to the environment;
        urea granule with very low ammonium salt concentration;
        cost benefits are achieved by reducing the ammonia and acid consumption;
        a simple way is used to process ammonia-laden gas streams in existing urea granulation plants;
        a proven and low-cost technical process is used to remove ammonia from the off-gas streams from the urea granulation plant with fluidized bed granulation;
        as the recovered ammonia is included in the product the urea production is increased, leading to a significant economic benefit; and
        a typical urea fertilizer grade product is produced.

## Claims

1. A urea granulation system comprising:
a urea granulator configured to generate granulated urea product and a first dust and ammonia-laden gaseous waste stream;
a first scrubber dust stage disposed downstream of, and in communication with, said urea granulator along a flow path of the first gaseous waste stream, said scrubber dust stage being configured to remove dust from the first dust and ammonia-laden gaseous waste stream, and convey the first gaseous waste stream downstream for further processing; and
a formaldehyde stage disposed downstream of, and in communication with, said scrubber dust stage along a flow path of the first gaseous waste stream, said formaldehyde stage being configured to receive the first gaseous waste stream and react a portion of the ammonia contained in the first gaseous waste stream with formaldehyde, so as to form hexamethylenetetramine.

2. The urea granulation system of claim 1 further comprising a scrubber acid stage disposed downstream of, and in communication with, said formaldehyde stage along a flow path of the first gaseous waste stream, said scrubber acid stage being configured to remove additional ammonia from said first gaseous waste stream and generate an ammonium salt waste stream.

3. The urea granulation system of claim 2 further comprising:
at least one product cooler in communication with said urea granulator, said product cooler being configured to cool granulated urea product conveyed to it from said urea granulator and generate a second dust and ammonia-laden gaseous waste stream; and
a second scrubber dust stage disposed downstream of, and in communication with, said product cooler along a flow path of the second dust and ammonia-laden gaseous waste stream, said second scrubber dust stage being configured to use the ammonium salt waste stream from said scrubber acid stage to remove ammonia from the second dust and ammonia-laden gaseous waste stream.

4. The urea granulation system of claim 1 further comprising:
an evaporation unit in communication with at least the first scrubber dust stage and configured to accept at least a dust laden liquid stream from the first scrubber dust stage and generate a concentrated liquor stream containing urea and ammonia salt; and
a conveyor in communication with said evaporation unit and configured to convey a urea melt to said evaporation unit.