NZ779411A - Process for producing biuret from urea - Google Patents
Process for producing biuret from ureaInfo
- Publication number
- NZ779411A NZ779411A NZ779411A NZ77941121A NZ779411A NZ 779411 A NZ779411 A NZ 779411A NZ 779411 A NZ779411 A NZ 779411A NZ 77941121 A NZ77941121 A NZ 77941121A NZ 779411 A NZ779411 A NZ 779411A
- Authority
- NZ
- New Zealand
- Prior art keywords
- urea
- section
- biuret
- ammonia
- solution
- Prior art date
Links
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 380
- 239000004202 carbamide Substances 0.000 title claims abstract description 190
- 238000000034 method Methods 0.000 title claims abstract description 68
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000243 solution Substances 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 claims abstract description 38
- 238000011084 recovery Methods 0.000 claims abstract description 31
- 238000002425 crystallisation Methods 0.000 claims abstract description 17
- 230000005712 crystallization Effects 0.000 claims abstract description 17
- 239000007790 solid phase Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 27
- 239000012452 mother liquor Substances 0.000 claims description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 24
- 238000004065 wastewater treatment Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000001569 carbon dioxide Substances 0.000 claims description 15
- 238000010790 dilution Methods 0.000 claims description 15
- ZFSLODLOARCGLH-UHFFFAOYSA-N Cyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 230000002194 synthesizing Effects 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 2
- 230000004048 modification Effects 0.000 claims 1
- 238000006011 modification reaction Methods 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 abstract 2
- 238000000354 decomposition reaction Methods 0.000 description 6
- BVCZEBOGSOYJJT-UHFFFAOYSA-N Ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 241000283690 Bos taurus Species 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- WNVQBUHCOYRLPA-UHFFFAOYSA-N triuret Chemical compound NC(=O)NC(=O)NC(N)=O WNVQBUHCOYRLPA-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Abstract
A process for the production of biuret from urea wherein: a urea aqueous solution (24) withdrawn from the recovery section of a urea plant is processed to remove water and obtain a concentrated urea melt (25); said urea melt is processed under biuret-forming conditions to decompose urea into biuret and ammonia and obtain a high-biuret urea melt (26); said high-biuret urea melt (26) is diluted with water or with an aqueous stream obtaining a solution (28); the solution (28) is subject to crystallization and precipitation of a solid phase containing biuret which is separated from the aqueous phase. and ammonia and obtain a high-biuret urea melt (26); said high-biuret urea melt (26) is diluted with water or with an aqueous stream obtaining a solution (28); the solution (28) is subject to crystallization and precipitation of a solid phase containing biuret which is separated from the aqueous phase.
Description
Process for producing biuret from urea
DESCRIPTION
Field of the invention
The present invention relates to a process for the production of biuret from urea.
The invention further relates to integration of a process for obtaining a product
which comprises predominantly biuret and urea with a conventional tion of
urea.
Prior Art
Urea is ed rially by reacting ammonia and carbon dioxide at suitable
urea-forming conditions, typically at a high re and high temperature.
Urea is synthesized at a synthesis pressure above 100 bar obtaining a reaction
effluent containing urea, water and unconverted ts mostly in the form of
ammonium carbamate. Due to the equilibrium reached in the reaction
environment, the amount of unconverted matter in the reaction effluent is
significant and the reaction effluent is ly processed for its recovery.
To this purpose, the reaction nt is normally processed in a recovery section
at a pressure lower than the synthesis pressure, ing a recycle solution
containing the reagents removed from the effluent, and a purified aqueous
on of urea. Said purified solution typically contains around 65-70% urea, the
balance being water and unavoidable impurities. The process of recovery
normally includes heating the on to decompose ammonium carbamate and
remove a gaseous phase containing ammonia and carbon dioxide, and
condensing said gaseous phase to obtain a recycle solution.
In the widely used stripping processes, the effluent of a high-pressure reactor is
heated in a high-pressure stripper, possibly in the presence of a stripping agent,
to decompose the ammonium carbamate and t gaseous ammonia and
carbon dioxide. These are condensed in a high-pressure condenser and recycled
to the sis reactor. When used, the stripping agent is generally gaseous
carbon dioxide or gaseous ammonia.
Said ressure stripper and high-pressure condenser may operate at
substantially the same pressure as the synthesis r, thus forming a highpressure
sis n or loop. The urea-containing nt of the stripper is
then sed in one or more recovery sections as described above.
Many applications require urea in a solid form. The production of solid urea is
also termed finishing or product-shaping.
The most common techniques for urea shaping include prilling and granulation.
In both cases, the purified urea solution from the recovery section is treated to
remove water, e.g. in a suitable evaporation section to obtain a urea melt.
Formaldehyde is also added to the urea melt before granulation or prilling, to
e the mechanical properties of the t, particularly the crushing
strength.
It is known that urea is subject to thermal decomposition into biuret and ammonia.
In the conventional production of urea, biuret is considered an undesired byproduct
and efforts are made to avoid its formation. Most applications of urea,
such as fertilizer-grade urea or technical-grade urea, require a content of biuret
not greater than 1.0% by weight.
The biuret, however, may be a valuable product for certain applications. For
example biuret is a useful source of non-protein nitrogen (NPN) for cattle feed.
The current production of biuret from urea involves basically dissolving the
commercial solid urea to form a urea melt, and maintaining the so obtained melt
in a batch reactor at a suitable temperature around 160 °C, deep vacuum and for
a suitable residence time for thermal decomposition of urea.
The above process is not suitable to e a high capacity of production.
Another disadvantage of the above process is that commercial solid urea
normally contains formaldehyde added during the shaping process.
dehyde poses serious health ns and may not be desired or not
ed e.g. in a rade biuret for cattle. Solid urea with no formaldehyde
(e.g. technical-grade urea) is expensive and available in limited quantity, thus not
adapted for a continuous process with a high capacity of production of biuret.
Furthermore a batch process as in the prior art is lly not suitable to e
a high capacity of production.
A method and device for preparing biuret is disclosed in US 2008/039623.
Summary of the invention
The invention aims to solve the above drawbacks. The invention aims to a
process adapted for production of biuret free of formaldehyde and adapted for a
high capacity of production.
The above problem is solved with a process according to claim 1.
According to the invention, a urea aqueous solution, which is withdrawn from the
recovery section of a urea production plant, is used for the production of highbiuret
urea (HBU). The term high-biuret urea denotes a product which consists
predominantly of biuret and urea. For example a HBU may contain at least 55%
by weight of biuret and preferably at least 70% by weight. The sum of biuret and
urea in the HBU at least 80% by weight.
The tion of HBU from the urea aqueous solution includes:
removing water, e.g. by evaporation, obtaining a urea melt preferably with
tration higher than 99.5 %wt, more preferably higher than 99.7 %wt;
processing the urea melt under biuret-forming conditions to decompose urea into
biuret and ammonia and obtain a biuret-containing urea melt;
diluting the biuret-containing urea melt with water or with an s stream
obtaining a solution;
crystallization of said solution, including precipitation of a solid phase containing
biuret and obtaining a slurry including precipitated solid phase and a mother
liquor;
separation of a solid product containing biuret from the slurry;
optionally, a further step of removing water from said solid product, e.g. with a
drying s.
The -containing solid t may be in the form of granules or powder.
The invention provides a process for the production of biuret which can be fully
integrated with a conventional urea process. By withdrawing urea solution from a
recovery section of a urea plant, the production of biuret can be coupled with the
tional production of low-biuret urea (LBU). The term low-biuret urea
denotes urea for uses wherein biuret is an red by-product. The content of
biuret in the LBU is typically not greater than 1.5% or 1.0% by weight.
The biuret can be produced in-line by continuously withdrawing urea solution from
the recovery section of a urea plant. Therefore the process of the invention is
suitable for a large capacity in terms of production, e.g. tons of biuret per day.
The integration with a urea production process is also advantageous for the
recycle of the ammonia liberated in the decomposition of urea. The
decomposition of urea into biuret produces also s ammonia which, in the
present invention, can be efficiently recycled to the tied-in urea production
process.
Still another advantage of the invention is that the urea solution withdrawn from
the recovery section can be sent to tion of biuret before any addition of
formaldehyde. Therefore a biuret free of dehyde can be ed in parallel
with the production of conventional LBU containing formaldehyde as a shaping
additive.
In a preferred embodiment, a first portion of the urea solution obtained from the
recovery section is processed to produce high-biuret urea and a second portion
of said solution is processed separately to produce conventional low-biuret urea.
The formaldehyde, if needed, can be added only to the second portion.
The invention further relates to a plant according to the . The plant is an
integrated plant for the tion of high-biuret urea and of low-biuret urea.
The invention can be applied to all processes for the production of urea including
in particular the total-recycle process and the stripping processes. The invention
can also be applied to an existing urea plant. An existing urea plant can be
modified by adding a high-biuret urea production section and by g at least
part of the on from the recovery section to the newly installed high-biuret
urea production section. A urea plant can be d for production of HBU in
parallel with the conventional production of LBU.
Description of preferred embodiments
The urea aqueous on used for the production of the HBU can be
substantially free of formaldehyde. ularly, this urea solution does not
contain added formaldehyde. If any, the content of formaldehyde in this solution
is preferably no more than 100 ppm by weight and more preferably no more than
50 ppm by weight.
The osition of urea may be performed by maintaining the urea melt in a
on space, which is ably maintained in a continuously stirred condition.
The reaction space may consist of a series of reaction volumes.
Said biuret-forming conditions may include one or more of the following: a
reaction temperature in the reaction space of 160 °C to 180 °C, preferably 160
°C to 170 °C and more preferably 165 °C; a residence time in the reaction space
that ranges from 30 min to 100 min, preferably 60 min; a pressure in the reaction
space which is heric pressure or below atmospheric pressure, preferably
slightly below atmospheric pressure.
The decomposition of urea into biuret produces also a gaseous ammonia. An
advantage of performing the decomposition at or about atmospheric pressure is
that such gaseous ammonia can be easily condensed with the addition of a
limited amount of water or with an aqueous process stream to produce an
ammonia solution. Said ammonia solution may contain preferably 10% to 20% of
ammonia. Said ammonia solution can be recycled to the urea plant to recover the
a contained therein. Another advantage is that no costly vacuum package
is then ed.
The decomposition of urea may be performed in a le biuret reactor, for
example a continuously stirred reactor. Said reactor may include a reaction
chamber surrounded by an interspace n hot steam is admitted to keep the
reaction space inside the reaction chamber at the desired reaction temperature.
The high-biuret urea melt obtained after osition of urea, e.g. awn
from the biuret reactor, typically ns by weight 16% of biuret, less than 3%
water and ties (mainly cyanuric acid and triuret), the balance being urea.
The solution obtained after dilution of the iuret urea melt may contain by
weight 40% to 60% of water, preferably 50%.
During crystallization, the solution is cooled down to a suitable temperature, for
example 5 °C, to obtain precipitation of biuret. The so obtained slurry is separated
into a solid phase and a mother liquor. Said mother liquor typically contains by
weight 2.0% to 3.0% of biuret, about 1.5% impurities (mainly cyanuric acid) and
40% to 50% urea.
The mother liquor from crystallization may be used as a cooling medium in a heat
exchanger to cool the solution before crystallization. The mother liquor, possibly
after this heat exchange step, may be recycled.
In an interesting embodiment the production of HBU is combined with the
production of conventional uret urea LBU. In that case, the urea solution
from the recovery section may be split between a section for the tion of
HBU and a section for the production of LBU.
A more advanced level integration between the two processes is possible. The
urea process typically includes a waste water treatment (WWT) section for the
treatment of water removed from the solution, e.g. in an ation section. This
WWT section usually encompasses a stripper/desorber to remove ammonia and
CO2 vapors and an hydrolyzer to convert urea to ammonia and CO2.
As result the WWT section produces a carbonate solution, which is recycled to
the urea recovery section, and an aqueous process condensate sent out of the
battery . In an embodiment of the ion this process condensate can be
used in the HBU n to dilute the high-biuret urea melt before crystallization
and to condensate the gaseous ammonia ed by the r. It has to be
noted this process condensate can be used in the HBU section as it is, without
the need to remove urea e.g. in a hydrolizer.
In a preferred embodiment of the invention the aqueous ammonia streams
produced by the HBU section are treated in a dedicated ammonia stripper to
remove ammonia and CO2 from the process condensate.
Said dedicated ammonia er is operated preferably at about 2.6 barg (bar
gauge) and provides the following streams: a carbonate solution which can be
recycled to the recovery section of the urea plant; a process condensate
cally free of ammonia and CO2 that can be used for dilution of the high-
biuret urea melt and/or for condensation of the ammonia released by the biuret
reactor. The amount of said process condensate which exceeds the HBU process
demand can be recycled to the WWT of urea plant.
More preferably said carbonate solution from the dedicated stripper may have a
water content up to 65%wt. Said process condensate may contain less than 500
ppm of ammonia and CO2 and up to 1.0%wt of urea.
A preferred embodiment includes that ammonia solution produced by
sation of the gaseous ammonia produced by the decomposition of urea is
subject to ammonia stripping in a dedicated ammonia stripper, thus obtaining an
s process condensate and a carbonate recycle solution. S aid recycle
solution is sent to the urea recovery section and a first n of said process
condensate is used for the above mentioned condensation of gaseous ammonia.
A second portion of said process condensate can be used to dilute the iuret
urea melt. Also a waste water d from the urea solution in the HBU section
can be treated in said ammonia stripper.
The use of a dedicated a stripper minimizes the impact of the HBU
section on the WWT section of the urea plant.
In a preferred embodiment the heat to the dedicated stripper is indirectly provided
by hot steam.
Dilution of the high-biuret urea melt with the process condensate from the WWT
section or the dedicated ammonia stripper can be made preferably with a ratio
1:1 of said melt and process condensate.
A portion of said process condensate from the WWT section or the dedicated
ammonia stripper can be used to help condensation of the gaseous a
removed from the biuret r. The ammonia solution obtained from such
condensation of ammonia is recycled to the WWT section or the dedicated
ammonia er, so that ammonia returns to the urea plant with the carbonate
solution.
Another preferred feature is the removal of cyanuric acid from the mother liquor
of crystallization. The mother liquor can be treated by adding an acid or carbon
dioxide to reduce the pH of the liquor and facilitates the precipitation of cyanuric
acid. Then the precipitated cyanuric acid can be removed for example by
centrifugation. The amount of acid or carbon dioxide is ably determined to
lower the pH of the liquor to 7.2 or less.
Use of carbon dioxide for said ent of the mother liquor offers a further
possibility of integration because CO2 is available as a source material for the
production of urea. A stream of CO2 can be taken from the CO2 feed of the plant,
for e from the delivery of the main CO2 compressor. The gaseous
ammonia is preferably absorbed in the mother liquor under pressure, preferably
at a pressure of about 5 bar abs. The mother liquor may be pumped at such
re if necessary.
The mother liquor, preferably after removal of cyanuric acid, can be recycled
internally in the HBU section. ably said mother liquor is recycled to the
water removal section (e.g. evaporator) of the HBU section. It must be noted that
the HBU section and the LBU section have separate water removal sections. By
recycling the mother liquor internally in the HBU n, a contamination of the
LBU section with biuret it is avoided.
It can be understood from the above that a remarkable advantage of the invention
is the strong integration between the production of conventional low-biuret urea
and the production of high-biuret urea.
Description of the figures
The invention and its advantages are now elucidated with the help of the figures
wherein:
Fig. 1 illustrates a scheme of a first embodiment of combined tion of lowbiuret
urea and high-biuret urea.
Fig. 2 is a variant of Fig. 1;
Fig. 3 is another variant of Fig. 1.
Fig. 4 is a variant of Fig.1 with dedicated ammonia stripper
Fig. 1 illustrates a plant including a urea synthesis section 1, a ry section
2, a high-biuret urea (HBU) section 3 and a low-biuret urea (LBU) section 4.
The HBU section 3 es a first evaporator 5, biuret reactor 6, crystallization
section 7 and a condenser 8.
The LBU section 4 includes: a second evaporator 9, finishing section 10, waste
water treatment section 11.
In Fig. 1, the following process streams are illustrated.
fresh carbon dioxide.
21 input of ammonia.
22 effluent from the synthesis section, which is typically a solution of urea, water
and unconverted ammonium carbamate.
23 urea solution from the recovery section 2, which is predominantly urea and
water with unavoidable ties.
24 first portion of the urea solution 23, directed to the HBU section 3.
urea melt obtained in the evaporator 5 and fed to the HBU reactor 6. Said urea
melt 25 typically contains more than 99% urea, e.g. 99.5% or more.
26 high-biuret urea melt obtained in the reactor 6. This melt may contain for
example 16% biuret.
27 dilution water.
28 solution obtained from dilution of the high-biuret urea melt 26. This solution
may contain for example 50% water, the e being biuret and urea.
29 solid product obtained in the crystallization section 7.
mother liquor from crystallization, which is sent back to the evaporator 5.
31 valve controlling the flow rate of the portion 24 of urea solution.
32 water removed in the evaporator 5, which is sent to the WWT n 11.
33 gaseous ammonia ed by the thermal decomposition of urea and
removed from the HBU reactor 6, which is sent to the a condenser 8.
34 water for sation of the ammonia 33.
ammonia solution recycled to the WWT section 11.
36 hot steam for heating the biuret r 6.
37 second portion of the urea on 23, which is directed to the LBU section 4.
38 low-biuret urea melt from the evaporator 9.
39 low-biuret urea, e.g granules or prills, produced in the finishing section 10.
40 water removed from the urea solution in the evaporator 9 and directed to the
WWT section 11.
41 recycle solution from the WWT section 11 sent to the recovery section 2.
42 carbamate-containing solution obtained in the recovery section 2 and sent
back to the synthesis section 1, e.g. to a high-pressure condenser.
Looking at Fig. 1 it can be appreciated that the urea solution 23 from the recovery
section 2 is split into first portion 24 and second portion 37. The first n 24 is
used in the HBU section 3 for production of the iuret urea 29; the second
portion 37 is used in the LBU section 4 for production of the low-biuret urea 39,
for example fertilizer-grade urea.
The high-biuret urea melt 26, having for example a content of biuret of about 70
wt%, is diluted with water 27 until it contains around 50% water. The so obtained
aqueous solution 28 is processed in the crystallization section 7 to obtain
precipitation of biuret. In the crystallization section 7, the solution may be suitably
, e.g. to around 5 °C, to obtain precipitation.
In the crystallization n 7, a slurry is obtained which is separated into a solid
phase and a liquid phase represented by a mother liquor. Optionally the
llization section 7 may e a drying section wherein the solid phase is
processed to further remove water. Hence a solid product 29 and a mother liquor
30 are obtained. The solid t 29 may be a granular product or a powder.
It has to be noted that each of the HBU section 3 and LBU section 4 has a
ted evaporator 5, 9. The provisio n of separate evaporators avoids
contamination with biuret of the line dedicated to the production of LBU.
The water 32 removed from the evaporator 5 of the HBU section 3 and the
a condensate 35 are recycled to the WWT section 11, providing a first
level of integration between the two sections 3 and 4.
The mother liquor 30 is recycled internally in the HBU n 3, by g the
feed of the evaporator 5, to avoid contamination of the LBU section, particularly
of the evaporator 9.
Fig. 2 is a variant providing a second level of integration wherein process
condensate from the WWT section 11 is used d of fresh water for diluting
the high-biuret melt and to promote sation of the ammonia removed from
the reactor 6.
A first stream 43 of an aqueous process condensate from said WWT section 11
is used for condensation of ammonia instead of water 34; a second stream 44 of
said process condensate is used to dilute the high-biuret melt 26 instead of water
Fig. 3 illustrates a third level of ation wherein a portion of the CO2 feed is
used to remove cyanuric acid from the mother liquor 30 before it is recycled to
the evaporator 5.
Particularly, a stream 45 of CO2 taken from the CO2 feed is absorbed in the liquor
, obtaining a liquor 46 at a lower pH wherein the cyanuric acid precipitates.
Then cyanuric acid is d from said liquor 46 in a centrifuge 47 obtaining
cyanuric acid solution 48 and a purified liquor 49 which is recycled to the
evaporator 5.
Fig. 4 illustrates a further embodiment including a dedicated stripper 50 for the
HBU unit 3. Said stripper 50 receives the water stream 32 and ammonia solution
and produces a process condensate 51. Said condensate 51 forms a
condensation stream 543 and the dilution stream 544 whose function is similar to
streams 43, 44 as above disclosed. Another part of said condensate 51 is sent to
the WWT section 11 as stream 52.
The stripper 50 additionally produces a second carbonate recycle solution 53
which is sent to the recovery section 2 in addition to the recycle solution 41.
The stripper 50 illustrated in Fig. 4 may be ented in all the ments
of the invention, for example the embodiment of Fig. 3. The er 50 may be
also integrated in the WWT section 11.
Claims (23)
1. A process for the production of biuret from urea comprising: a) ammonia and carbon dioxide are reacted in a sis section (1) at a synthesis pressure to form urea and obtaining a reaction effluent 5 (22) containing urea, water and unconverted reagents; b) said on effluent is processed in a recovery n (2) to recover unconverted reagents contained therein; c) a urea aqueous on (24), withdrawn from the recovery section, is processed to remove water and obtain a concentrated urea melt (25); 10 d) said urea melt is processed under biuret-forming conditions to decompose urea into biuret and ammonia and obtain a high-biuret urea melt (26); e) said high-biuret urea melt (26) is diluted with water or with an aqueous stream obtaining a solution (28); 15 f) the solution (28) obtained at step e) is subject to a process of crystallization including precipitation of a solid phase containing biuret and obtaining a slurry including precipitated solid phase and a mother g) the slurry obtained at step f) is processed to obtain a -containing 20 solid product (29) and a mother liquor (30).
2. s according with claim 1 wherein the step g) includes separation of a solid phase from the slurry and further processing of said solid phase to remove residual water.
3. A process according to claim 1 or 2 wherein the solid product obtained after 25 step g) contains at least 55% by weight of biuret, preferably at least 70% by weight.
4. A process according to any of the previous claims wherein the sum of biuret and urea in the solid product obtained after step g) is at least 80% by weight.
5. A process according to any of the previous claims wherein step d) is performed by maintaining the urea melt in a reaction space, which is preferably maintained in a continuously stirred condition. 5
6. A process according to claim 5 wherein the biuret-forming conditions of step d) include one or more of: a reaction temperature in the reaction space of 160 °C to 180 °C, preferably 160 °C to 170 °C and more preferably 165 °C; a nce time in the on space that ranges from 30 min to 100 min; 10 a pressure in the reaction space which is heric pressure or slightly below atmospheric pressure.
7. A process according to any of the previous claim wherein the urea aqueous solution (24) of step c) is substantially free of formaldehyde, preferably containing no more than 100 ppm by weight of formaldehyde. 15
8. A process according to any of the previous claims wherein: the urea aqueous solution (24) of step c) is a first n of a solution (23) obtained from the recovery section (2); a second portion (37) of urea aqueous solution from the recovery section is processed to remove water, tely from the first portion, obtaining a urea melt (38); said urea melt obtained from the second 20 portion of the solution is processed for the production of low-biuret urea (39).
9. A process according to any of the previous claims wherein the solution obtained after dilution of step e) contains by weight 40% to 60% of water, preferably 50%.
10. A process according to any of the previous claims wherein gaseous a 25 (33) obtained at step d) is condensed obtaining an a on (35) and ammonia contained in said solution is recycled to the urea process.
11. A process according to claim 10 wherein said gaseous ammonia (33) is condensed with process condensate (43) from a waste water treatment section (11) and the ammonia solution (35) is recycled to said waste water treatment section. 5
12. A process according to claim 10 n the ammonia solution (35) is subject to ammonia stripping in a dedicated a stripper (50), thus obtaining an aqueous process condensate (51) and a carbonate recycle solution (53); said e solution (53) is sent to the urea ry section; a first n of said process sate is used for condensation of said gaseous a (33). 10
13. A process according to claim 12 wherein: a waste water obtained at step c) is d in said ammonia stripper (50) and a second portion (44) of said process condensate is used in step e) to dilute the high-biuret urea melt (26).
14. A process according to any of the previous claims n the mother liquor (30) obtained at step f) is treated by adding an acid or carbon dioxide to 15 reduce the pH of the liquor, preferably to 7.2 or less, and cause the precipitation of cyanuric acid contained in the liquor, and the precipitated cyanuric acid is removed.
15. A process according to claim 14 wherein the mother liquor is treated by absorption of gaseous carbon dioxide and the absorption is performed under 20 re, preferably at a pressure of about 5 bar abs.
16. A process according to any of the previous claims wherein the mother liquor of step f), preferably after removal of cyanuric acid, is mixed with the urea solution of step c) before the water removal step.
17. A plant for producing biuret with a process in accordance with any of the 25 previous claims, the plant comprising: a high-pressure urea synthesis section (1) configured to react ammonia and carbon dioxide to obtain a reaction effluent containing urea, water and unconverted reagents; a recovery section (2) configured to recover unconverted reagents contained in the effluent of the synthesis section; a section (3) for the production of high-biuret urea which ses: 5 a first water removal section (5), which is preferably an evaporation section, configured to remove water from a stream (24) of urea aqueous solution withdrawn from the recovery section, and to obtain a concentrated urea melt (25); a biuret reactor (6) arranged to process said urea melt (26) under biuret- 10 forming ions to decompose urea into biuret and ammonia and obtain a high-biuret urea melt (26); a line (27, 44) arranged to add water or an aqueous stream to said biuretcontaining urea melt at a dilution point, ing a solution (28); a crystallization section (7) arranged to process said solution obtained after 15 the dilution of the melt and to obtain a slurry including itated solid phase and a mother liquor, and to s the slurry obtaining a solid phase (29) separated from a liquid phase (30); optionally a drying section adapted to further remove water from the solid phase for conversion into a granular product or a powder. 20
18. A plant according to claim 17 further comprising a shaping section (4) for the production of low-biuret urea, n said shaping section includes a second water removal section (9), which is separate from said first water removal section, the plant comprising a first line ed to feed a first portion (24) of urea aqueous solution from the recovery section to said 25 section for high-biuret urea a and a second line arranged to feed a second portion (37) of said urea aqueous solution to said section for low-biuret urea.
19. A plant according to claim 17 or 18, comprising a waste water treatment section (11) for the treatment of waste water withdrawn from said second water removal section, and further comprising a line (44) arranged to feed a process condensate from said water treatment section to said dilution point of the high-biuret urea section for dilution of the biuret-containing urea melt. 5
20. A plant according to claim 19 wherein the high-biuret urea section ses an ammonia condenser (8) and a line ed to feed gaseous ammonia (33) removed from the biuret reactor (6) to said ammonia condenser, the plant further sing a line (43) arranged to feed a process condensate from said waste water treatment section (11) to said a ser (8), 10 and a line (35) arranged to feed ammonia solution from the ammonia condenser to said waste water treatment section.
21. A plant according to any of claims 17 to 20, comprising an ammonia stripper (50) for the treatment of waste water (32) withdrawn from said first water removal section (5), and further comprising at least one of: 15 a line (544) arranged to feed a process sate from said ammonia er (50) to said dilution point of the high-biuret urea section for dilution of the biuret-containing urea melt (26); a line (543) arranged to feed a process condensate from said ammonia stripper (50) to an ammonia condenser (8) of gaseous a from the 20 biuret reactor, and a line (35) arranged to feed ammonia solution from the ammonia condenser to said ammonia stripper.
22. A plant according to any of claims 17 to 21, wherein the high-biuret urea section includes a section for removal of cyanuric acid from the mother liquor awn from the crystallization section, and the plant includes a line 25 arranged to add an acid to said mother liquor or a line arranged to add carbon dioxide to said mother liquor, the carbon dioxide being taken from the carbon dioxide feed of the plant.
23. A method of modifying a urea plant wherein: the urea plant, before modification, comprises at least: a high-pressure urea synthesis section (1); a recovery section (2); a uret urea section (4) arranged to convert a urea aqueous solution taken from the recovery 5 section into solid urea, said low-biuret urea section including at least a water removal section (9) to remove water from the on and obtain a urea melt, and a shaping section (10) to convert the urea melt into solid urea; the method includes adding a high-biuret urea section (3) including at least: 10 a dedicated water removal section (5), configured to remove water from a stream of urea aqueous on and to obtain urea melt; a biuret reactor (6) arranged to process said urea melt under biuret-forming ions to decompose urea into biuret and ammonia and obtain a biuretcontaining urea melt; 15 a line (27, 44) arranged to add water or an aqueous stream to said biuretcontaining urea melt at a dilution point, ing a solution; a llization section (7) arranged to process said solution ed after the dilution of the melt and to obtain a slurry including precipitated solid phase and a mother liquor and to process the slurry obtaining a solid phase 20 separated from the liquid phase; optionally, a drying section adapted to further remove water from said solid phase for the obtainment of a granular product or a powder; the method further comprising the provision of a line (24) arranged to feed a portion of the aqueous on from the recovery section to the newly 25 installed high-biuret urea section.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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EP20208473.7 | 2020-11-18 |
Publications (1)
Publication Number | Publication Date |
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NZ779411A true NZ779411A (en) | 2021-08-27 |
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