USOO7674932B2

(12) United States Patent (10) Patent No.: US 7,674,932 B2

Davey et al. (45) Date of Patent: Mar. 9, 2010
(54) METHOD FOR THE PRODUCTION OF UREA (52) U.S. Cl. ............................. 564/63:564/69;564/70;
FROMINATURAL. GAS 564/72
(58) Field of Classification Search ................... 564/63,
(75) Inventors: William Davey,
y Frankfurt am Main 564/67, 69, 72
R Thomas Wurzei, Oberursel/Ts See application file for complete search history.
(56) References Cited
(73) Assignee: Lurgi AG, Frankfurt am Main (DE) U.S. PATENT DOCUMENTS
(*) Notice: Subject to any disclaimer, the term of this 4,409, 196 A 10/1983 Skinner et al. .............. 423,359
patent is extended or adjusted under 35 6,231.827 B1 5/2001 Pagani et al. .......... ... 423,359
U.S.C. 154(b) by 54 days. 6,448,441 B1 9/2002 Wing-Chiu et al. ........... 564f67
2004/0028595 A1 2/2004 Davey et al.
(21) Appl. No.: 11/665,278
(22) PCT Fled: Aug. 18, 2005 Primary Examiner Peter G. O'Sullivan
(74) Attorney, Agent, or Firm—Jonathan Myers; Andrew
(86). PCT No.: PCT/EP2005/008936 Wilford
S371 (c)(1), (57) ABSTRACT
(2), (4) Date: Nov. 29, 2007
Disclosed is a method for the production ofurea from natural
(87) PCT Pub. No.: WO2006/039960 gas, wherein a) natural gas undergoes partial oxidation or
autothermal reformation with a gas containing oxygen in a
PCT Pub. Date: Apr. 20, 2006 first step and the raw synthesis gas thus arising, consisting
essentially of carbon monoxide, carbon dioxide, methane and
(65) Prior Publication Data hydrogen, can be transformed by catalytic conversion of CO
US 2008/O2O7948A1 Aug. 28, 2008 and HO to form CO, and H, whereupon carbon monoxide
and methane are removed in a multistep gas cleaning process
(30) Foreign Application Priority Data and the hydrogen is converted into ammonia upon addition of
Oct. 12,s 2004 (DE) ....................... 10 2004 049 774 nitrogen, and subsequently, b) the ammonia is recombined
with the previously separated carbon dioxide in a second step
(51) Int. Cl. and the ammonia is thus fully converted into urea.
C07C 273/02 (2006.01)
C07C 237/04 (2006.01) 3 Claims, 2 Drawing Sheets
 US 7,674,932 B2
1. 2
METHOD FOR THE PRODUCTION OF UREA The inventive method for the catalytic production of
FROMINATURAL. GAS ammonia from a nitrogen/hydrogen mixture, used in the first
method step, was described in German patent 100 55818 US
CROSS REFERENCE TO RELATED 2004/0028595.In it, natural gas together with an oxygen-rich
APPLICATIONS gas are conducted into an autothermal reformer where a raw
synthesis gas is produced attemperatures ranging from 900 to
This application is the US national phase of PCT applica 1200°C., a pressure of 40 to 100 bar, and in the presence of a
tion PCT/EP2005/008936, filed 18 Aug. 2005, published 20 catalyst. This synthesis gas, calculated dry, has an H2 content
Apr. 2006 as WO 2006/039960, and claiming the priority of of 55 to 75 percent by volume, a CO content of 15 to 30
German patent application 102004.049774.5 itself filed 12 10 percent by volume, a CO content of 5 to 30 percent by
Oct. 2004. volume, and a H:CO volume ratio of 1.6 to 4. The raw
The invention relates to a two-step method for producing synthesis gas is then drawn out of the autothermal reformer,
urea from natural gas, where in a first method step ammonia cooled, conducted through a catalytic conversion for convert
and carbon dioxide are produced, and in a second method step ing the CO to H, and a converted synthesis gas with a H.
they are reacted with one another to form urea. In particular, 15 content, calculated dry, of no less than 55 percent by volume
the invention relates to producing Stoichiometric and Supers and a CO content of no more than 8 percent by volume is
toichiometric quantities of urea from natural gas. drawn off. The converted synthesis gas is then Subjected to a
It is known that it is possible to produce urea from natural multistep gas purification for removing CO, CO, and CH
gas in a two-step method. and a nitrogen/hydrogen mixture is produced that is catalyti
In a first step, nitrogen is bound as ammonia, and at the cally converted to ammonia.
same time carbon dioxide is produced from the natural gas, In general the natural gas used as the starting material
while in a second method step the ammonia and the carbon largely comprises methane. In this case, the quantity of car
dioxide are converted to urea. It is also known that the quan bon dioxide obtained therefrom is stoichiometrically
tity of urea that can be produced using this method is limited adequate for converting to urea ammonia formed in the first
by the quantity of carbon dioxide that can be obtained in the 25 step of the inventive method. In this case, then, there will be
first method step. no excess of ammonia. However, if the starting material also
Normally, in the first method step, that is the ammonia contains larger quantities of higher hydrocarbons, which is
synthesis, a synthesis gas is produced from natural gas, and an frequently the case, then the quantity of the carbon dioxide
oxygen-containing gas, e.g. air, in a steam reformer, and then formed in the first step of the inventive method exceeds the
in a further method step (“secondary reformer') the oxidation
30 stoichiometrically required quantity by up to 10%. This
of the carbohydrates contained in the natural gas is largely means that additional ammonia can be added to the reaction,
concluded. This method leads to a synthesis gas, whose car either from an adjacent system or from purchased supplies,
bon dioxide content is about 10% less than is stoichiometri which then causes the quantity of the inventively formed urea
cally required for converting the simultaneously resulting to exceed that of a conventional system for ammonia produc
ammonia to urea. Therefore all such methods for producing
35 tion by up to 20%. This demonstrates the significantly
urea involve the problem of how to use the excess ammonia. improved efficiency of the inventive method for producing
urea compared to all previously known methods for produc
A new method has now been found in which the quantity of ing urea from natural gas.
the carbon dioxide produced using partial oxidation of the For the first step of the inventive method it is important that
natural gas is equal to or greater than the stoichiometric 40 a system for steam reforming is not used when producing the
quantity that is required for converting the ammonia to urea. raw synthesis gas. Instead, in accordance with the invention
With this method it is therefore possible not only to convert all an autothermal reformer is used that works at relatively high
of the resultant ammonia to urea, but it is also even possible to pressures that range from 30 to 100 bar, and primarily
produce large enough quantities of carbon dioxide to convert between 40 and 80 bar. Downstream of the autothermal
additional ammonia that has been added from an external 45 reformer this high pressure can be maintained approximately
ammonia Source, which means in accordance with the inven so that the synthesis gas only has to be compressed slightly
tion a Substantially higher quantity of urea can be produced prior to beginning the ammonia synthesis. This is signifi
than with conventional methods.
cantly more cost effective compared to conventional methods
The subject of the invention is therefore a method for with Steam reforming, in which only relatively low pressures
producing urea from natural gas in which: 50 are permitted. Compared to steam reforming, the autothermal
a) in a first method step natural gas and an oxygen-contain reformer has the additional advantage that it provides a gas
ing gas are Subjected to partial oxidation or to autothermal with an adequate H2/CO ratio, so that, as already mentioned
reformation and the resultant raw synthesis gas, largely com in the foregoing, after the conversion with the CO occurring
prising carbon monoxide, carbon dioxide, methane, and in the gas purification, all of the NH produced can be con
hydrogen, is converted from CO and HO to CO and H 55 verted to urea.
using catalytic conversion, thenina multistep gas purification Thus, in the inventive method, in the first method step a
carbon dioxide, carbon monoxide, and methane are removed catalytic conversion is performed in which the carbon mon
from the synthesis gas and, after the addition of nitrogen, the oxide and HO are converted to CO and H. This is then
remaining hydrogen is catalytically converted to ammonia, followed by a multistage gas purification for removing carbon
and then 60 dioxide, carbon monoxide, and methane. A washing process
b) in a second method step the ammonia is recombined in which e.g. methanol is used attemperatures ranging from
with the previously separated carbon dioxide and all of the -20 to -70° C. is particularly advantageous. Only relatively
ammonia is converted. little energy, including compression energy, is used for this.
In particular, however, it is possible in the second method It is useful when the oxygen-rich gas added to the autother
step to also add NH from an external ammonia Source Such 65 mal reformer has an oxygen content of no less than 70 percent
that all of the excess carbon dioxide formed in the first step by volume and in general even no less than 90 percent by
can be converted to urea. Volume. In this manner the content of impurities in the Syn
 US 7,674,932 B2
3 4
thesis gas is reduced and the washing step can be reduced. The The invention claimed is:
hydrogen to CO. volume ratio for the synthesis gas leaving 1. A method for producing urea from natural gas wherein
the conversion is preferably 2 to 3 (dry calculation). a) in a first method step natural gas and a an oxygen
The block diagrams attached as FIG. 1 and FIG. 2 demon containing gas is Subjected to partial oxidation or to
strate the advantages of the inventive method compared to a autothermal reformation and the resultant raw synthesis
method in accordance with the prior art. FIG. 1 shows the gas, largely comprising carbon monoxide, carbon diox
prior art. In accordance with this method, a gas mixture made ide, methane, and hydrogen, is converted from CO and
of ammonia and carbon dioxide is produced from natural gas HO to CO and H. using catalytic conversion, then in a
and air in the first method step, but it contains 10% less carbon multistep gas purification carbon dioxide, carbon mon
dioxide than is required for Stoichiometric conversion to urea. 10
oxide, and methane are removed and, after the addition
Excess ammonia must therefore be removed from the system. of nitrogen, the hydrogen is catalytically converted to
Steam reforming and Subsequent second reforming charac ammonia, and then
terize the conventional method.
In contrast, FIG. 2 depicts the inventive method in which b) in a second method step the ammonia is recombined
partial oxidation or autothermal reformation is used, as is with the previously separated carbon dioxide and NH
from an external ammonia Source is added Such that all
described in German patent application 100 55 818. In this of the carbon dioxide is converted to urea.
method ammonia added from outside can be used to bond the
2. The method in accordance with claim 1 wherein the
excess carbon dioxide formed. This causes substantial quan oxygen-containing gas used for the partial oxidation has an
tities of additional urea to be formed.
Special advantages of the inventive method result when the oxygen content of no less than 70 percent by Volume.
inventive method is combined e.g. with an adjacent system 3. The method in accordance with claim 1 wherein the
for methanol synthesis from natural gas. Such a system pro synthesis gas leaving the conversion has a hydrogen:CO
duces plenty of excess carbon dioxide that can be added to the volume ratio of 2 to 3 (dry calculation).
inventive method and with ammonia from an external Source
contributes to further increasing the yield of urea.
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. 7,674,932 B2 Page 1 of 1
APPLICATION NO. : 1 1/665278
DATED : March 9, 2010
INVENTOR(S) : William Davey et al.
It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

On the Title page, Item (75) the correct spelling of the second inventors name is:
-- Thomas Wurzel --

Signed and Sealed this

Eleventh Day of May, 2010

David J. Kappos
Director of the United States Patent and Trademark Office