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.

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.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The present disclosure is described in detail below with reference to the attached drawing figures.

(2) FIG. 1 is a schematic block diagram of an embodiment of a urea granulation process utilizing an ammonia formaldehyde convert process, as disclosed herein.

(3) 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.

(4) 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

(5) 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.

(6) 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).

(7) 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.

(8) 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.

(9) 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.

(10) 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.

(11) 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.

(12) 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.

(13) 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.

(14) 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.

(15) 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.

(16) 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.

(17) 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.

(18) 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.

(19) 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.

(20) 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.

(21) 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.

(22) Optionally a portion of urea melt 22 is fed into the evaporation unit 16.

(23) Furthermore the clean off-gas 6 is released into the atmosphere and exhibits a concentration of NH.sub.3 in the range of 5-30 mg/Nm.sup.3, and preferably exhibits a concentration of NH.sub.3 being <10 mg/Nm.sup.3.

(24) 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,

(25) whereby the scrubber dust stage 11 is arranged upstream of the formaldehyde stage 2.

(26) Furthermore an additional scrubber acid stage 3 is integrated into the scrubbing system downstream of the formaldehyde stage 2.

(27) 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.

(28) 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.

(29) Furthermore the apparatus comprises means for conveying a portion of urea melt to the evaporation unit 16.

(30) With advantage scrubbers used in the current technology are horizontal scrubbers.

(31) 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.

(32) 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.

(33) 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.

(34) 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.

(35) 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.

(36) 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

(37) 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.

(38) In a urea granulation process with formaldehyde scrubbing a formaldehyde-containing solution is added to the ammonia-laden air or the formaldehyde stage.

(39) 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.

(40) 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.

(41) 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/Nm.sup.3 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/Nm.sup.3 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/Nm.sup.3 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/Nm.sup.3 with a minor amount of acid to be used. Therefore a drastically improvement can be achieved using this technology.

(42) TABLE-US-00001 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/Nm.sup.3 mg/Nm.sup.3 mg/Nm.sup.3 mg/Nm.sup.3 combined stack □ 0.6 to 0.7 □ 0.40 □ 0.14 □ 0.05 kg/ton.sub.product kg/ton.sub.product kg/ton.sub.product kg/ton.sub.product Formaldehyde 45.00% 75.00% 75.00% efficiency Ammonium ≅0.35 sulphate produced kg/ton.sub.product

(43) 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

(44) 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.

(45) 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.

(46) 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.

(47) TABLE-US-00002 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/Nm.sup.3 mg/Nm.sup.3 mg/Nm.sup.3 combined stack ≅0.6 to 0.7 ≅0.05 ≅0.05 kg/ton.sub.product kg/ton.sub.product kg/ton.sub.product Sulphuric acid ≅2.0 ≅0.27 consumption kg/ton.sub.product kg/ton.sub.product Ammonium sulphate ≅2.3 ≅0.35 produced kg/ton.sub.product kg/ton.sub.product

(48) 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.

(49) 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.