US008398842B2

(12) United States Patent

Aulich et al.

(10) Patent N0.: (45) Date of Patent:

(56)

US 8,398,842 B2
*Mar. 19, 2013

(54)

ELECTROCHEMICAL PROCESS FOR THE PREPARATION OF NITROGEN FERTILIZERS

References Cited
U.S. PATENT DOCUMENTS
2,135,733 A * 11/1938 Richardson ................. .. 423/392

(75) Inventors: Ted R. Aulich, Grand Forks, ND (US);

Edwin S. Olson, Grand Forks, ND (US); Junhua Jiang, Grand Forks, ND (US)

(Continued)
FOREIGN PATENT DOCUMENTS
EP 972855 Al * l/2000

(73) Assignee: Energy & Environmental Research

Center Foundation, Grand Forks, CA

EP

0972855 Al

l/2000

(Us)
Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35

(Continued)
OTHER PUBLICATIONS
Shibata et al., Electrochemical Synthesis of Urea at Gas-Diffusion

U.S.C. 154(b) by 0 days.

This patent is subject to a terminal dis claimer.

Electrodes, J. Electrochem. Soc. (Feb. 1998), vol. 145, No. 2, pp.

595-600.*

(Continued)
Primary Examiner * Edna Wong

(21) Appl. N0.: 13/420,979 (22) (65)

Filed: Mar. 15, 2012
Prior Publication Data

(74) Attorney, Agent, or Firm * Conley Rose, P.C.; Rodney

B. Carroll

US 2012/0234689 A1

Sep. 20, 2012

(57)

ABSTRACT

The present invention provides methods and apparatus for the

Related US. Application Data

preparation of nitrogen fertilizers including ammonium

nitrate, urea, urea-ammonium nitrate, and/or ammonia utiliZ
ing a source of carbon, a source of nitrogen, and/or a source of

(63)

Continuation of application No. 12/200,621, ?led on

Aug. 28, 2008, noW Pat. No. 8,152,988. (60) Provisional application No. 60/969,341, ?led on Aug. 31, 2007.

hydrogen. Implementing an electrolyte serving as ionic charge carrier, (1) ammonium nitrate is produced via the
reduction of a nitrogen source at the cathode and the oxidation of a nitrogen source at the anode; (2) urea or its isomers are produced via the simultaneous cathodic reduction of a carbon

(51)

Int. Cl.

C25B 1/00 C25B 1/22 C25B 3/00

(2006.01) (2006.01) (2006.01)

205/455

source and a nitrogen source; (3) ammonia is produced via the reduction of nitrogen source at the cathode and the oxidation of a hydrogen source at the anode; and (4) urea-ammonium

(52) (58)

US. Cl. ...... .. 205/551; 205/552; 205/553; 205/431;

Field of Classi?cation Search ................ .. 205/ 551,

nitrate is produced via the simultaneous cathodic reduction of

a carbon source and a nitrogen source, and anodic oxidation of a nitrogen source. The electrolyte can be solid.

205/552, 553, 431, 455 See application ?le for complete search history.

17 Claims, 12 Drawing Sheets

Cold trap
36

US 8,398,842 B2
Page 2
US. PATENT DOCUMENTS
4,163,775 A 4,749,462 A 5,736,016 A
5,744,009 A *

OTHER PUBLICATIONS
Foreign communication from a related counterpart applicationi International Preliminary Report on Patentability, PCT/US2008/ 074859, Mar. 2, 2010, 6 pages. Foreign communication from a related counterpart applicationi International Search Report and Written Opinion, PCT/US2008/

8/1979 Foster et al. 6/1988 Bachot et al. 4/1998 Allen

4/1998 Singh et al. ................... .. 203/42

7,314,544 B2 7,846,319 B2
8,152,988 B2*

1/2008 Murphy et al. 12/2010 Koyamaet al.

4/2012
1/2004

Aulich et al. ............... .. 205/551

Petillo et a1. ................ .. 429/122

2002/0031694 A1
2004/0009392 A1*

3/2002 Van Berkelet al.

074859, Apr. 15, 2009, 7 pages.

Foreign communication from a related counterpart applicationi International Search Report and Written Opinion, PCT/US2011/ 056308, Jul. 11, 2012, 7 pages. Provisional patent application entitled Electrochemical Process for

2006/0049063 A1* 2011/0120880 A1*

3/2006 5/2011

FOREIGN PATENT DOCUMENTS

GB 2096124 A * 10/1982

the Preparation of Nitrogen Fertilizers, by Junhua Jiang, et al., ?led

Aug. 31, 2007 as US. Appl. No. 60/969,341. Foreign communication from a related counterpart applicationi Written Opinion, PCT/US2011/056308, Dec. 13, 2012, 5 pages.

JP
W0

11347558 A
WO 2006061082 A1 *

12/1999
6/2006

WO WO WO

2009029839 A2 2009029839 A3 2012051507 A2

3/2009 3/2009 4/2012

* cited by examiner

US. Patent

Mar. 19, 2013

Sheet 1 0112

US 8,398,842 B2

NH3 + HND3
) NH4ND3

16

US. Patent

Mar. 19, 2013

Sheet 2 0f 12

US 8,398,842 B2

NH3 + Hm:3
} NH4NO3

16

FIG. 2

US. Patent

Mar. 19, 2013

Sheet 3 0f 12

US 8,398,842 B2

NH3+HN03

19TNH4N03
15 I

NH3I
26

US. Patent

Mar. 19, 2013

Sheet 4 0f 12

US 8,398,842 B2

1?

19 * Ham's3
H3 + 16

NHS
29 10

15

N0+H2G

FIG. 4

US. Patent

Mar. 19, 2013

Sheet 5 0f 12

US 8,398,842 B2

11

4:
0
Z

:>
+N
O
U

CO(NH

_ 9

co2+No_>
| |

{- H2

FIG. 5

US. Patent

Mar. 19, 2013

Sheet 6 0f 12

US 8,398,842 B2

FIG. 6

US. Patent

Mar. 19, 2013

Sheet 7 0f 12

US 8,398,842 B2

FIG. 7

US. Patent

Mar. 19, 2013

Sheet 8 0f 12

US 8,398,842 B2

14
13

_15

i:
E,

a
+

5"

Elliu

U kil

I
_II

q:
I
+

I
2

O Z

5* U

12

FIG. 8

US. Patent

Mar. 19, 2013

Sheet 9 0f 12

US 8,398,842 B2

Cold trap
36

CO2+NO

FIG. 9

US. Patent

Mar. 19, 2013

Sheet 10 0f 12

US 8,398,842 B2

CD2+ N0+ H2

FIG. 10

US 8,398,842 B2
1
ELECTROCHEMICAL PROCESS FOR THE PREPARATION OF NITROGEN FERTILIZERS CROSS-REFERENCE TO RELATED APPLICATIONS

2
equilibrium conversion of hydrogen gas and nitrogen gas to
ammonia is generally only on the order of 10%~15%. LoW

conversion ef?ciencies give rise to cost-intensive, large-scale chemical plants and costly operating conditions required to
commercially produce hundreds to thousands of tons per day of ammonia in an ammonia synthesis plant. Ammonium nitrate (AN) is produced via the acid-base reaction of ammonia With nitric acid according to the equa
tion:

This is a Continuation Application of US. patent applica tion Ser. No. 12/200,621 ?led Aug. 28, 2008, published as
US. 2009/0057161 A1, and entitled Electrochemical Pro cess for the Preparation of Nitrogen Fertilizers, now US. Pat. No. 8,152,988, Which claims the bene?t under 35 U.S.C.

119(e) of US. Provisional Patent Application No. 60/969,

341 entitled Electrochemical Process for the Preparation of

Nitrogen Fertilizers, ?led Aug. 31, 2007, the disclosures of Which are hereby incorporated herein by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
20

Industrial nitric acid is manufactured by the high-tempera ture catalytic oxidation of ammonia. This process typically consists of three steps: ?rst, ammonia is reacted With air on PtIr alloy catalyst at around 7500 ~800 C. to form nitric oxide according to the folloWing reaction:
Next, nitric oxide is oxidized to nitrogen dioxide and its liquid
dimer as folloWs:

This invention Was made With US. Government support

under Contract No. DE-FC36-03GO13055 aWarded by the US. Department of Energy, and Contract Nos. 2003 -3881 9

And, ?nally, the nitrogen di oxide/dimer mixture is introduced

into an absorption process using Water in accordance With the
25

02014, 2004-38819-02182, 2005-38819-02311, and 2006 38819-03470 aWarded by the US. Department of Agricul
ture. The Government has certain rights in this invention.
BACKGROUND OF THE INVENTION

folloWing reaction:
In the ?rst step, the oxidation of ammonia to nitric oxide
proceeds in an exothermic reaction With a range of 93% to 98% yield. Reaction temperatures can vary from 750 C. to

1. Field of the Invention

This invention relates to an electrochemical method and

30

apparatus for the synthesis of nitrogen fertilizers including

ammonium nitrate, urea, ammonia, and urea-ammonium
nitrate. In particular, the invention relates to an apparatus and method Whereby (1) a nitrogen source is utilized to produce ammonium nitrate; (2) a nitrogen source and a carbon source are reacted using liquid electrolyte at loW temperature or solid
35

electrolyte at high temperature to form urea; (3) a nitrogen

source and a hydrogen-equivalent source are reacted to gen

erate ammonia; and (4) a nitrogen source and carbon source are reacted to produce urea-ammonium nitrate.

9000 C. Higher temperatures increase reaction selectivity toWard NO production. Reaction 3 is favored by loW pres sures. In the second step, Reaction 4 is sloW and highly temperature- and pressure-dependent. Operating at loW tem peratures and high pres sures promotes maximum production of NO2 Within a minimum reaction time. The ?nal step, Reac tion 5, is exothermic, and continuous cooling is therefore required Within the absorber. As the conversion of NO to NO2 is favored by loW temperature, this reaction Will take place signi?cantly until the gases leave the adsorption column.
The commercial production of urea is based on the reaction

40

2. Background of the Invention Ammonium nitrate (AN, 34% N), urea (46% N), ammonia

of carbon dioxide and ammonia at high pressure (for example

(82% N) and urea-ammonium nitrate (UAN, 28%~32% N)

are Widely used high nitrogen-content fertilizers. Methods for
industrial production of these fertilizers are mainly based on the Haber process, Which involves the heterogeneous reaction of nitrogen and hydrogen on an iron-based catalyst at high
45

140 bar) and high temperature (for example 180 ~185 C.) to form ammonium carbamate (Reaction 6), Which is subse quently dehydrated into urea and Water (Reaction 7):

pressure (for example, 200-300 bar) and high temperature

(for example, 4300 C.-480 C.) to produce ammonia as fol
loWs:
50

Reaction 6 is fast and highly exothermic and goes essen

tially to completion under normal processing conditions,

While Reaction 7 is sloW and endothermic and usually does not reach thermodynamic equilibrium under processing con ditions. The degree to Which Reaction 7 proceeds depends on, among other factors, the temperature and the amount of excess ammonia used. Increasing temperature and the NH3: CO2 ratio could increase the conversion of CO2 to urea. Different urea production technologies basically differ on hoW urea is separated from the reactants and hoW ammonia and carbon dioxide are cycled. Re?nements in the production technology are usually concentrated on increasing CO2 con

The conversion to ammonia, shoWn in Reaction 1, is lim ited by thermodynamics. The gas volume decreases as the reaction progresses. Hence, very high pressure must be used to drive the ammonia synthesis reaction to the right in Reac tion 1, Which is in the direction of ammonia gas. Carrying out ammonia synthesis at very high pressure is also necessary to

55

prevent decomposition of synthesized ammonia into nitrogen

and hydrogen and to provide practical reaction rates. In addi tion, Reaction 1 is exothermic, and ammonia formation increases With decreasing temperature. Reducing the tem perature, hoWever, undesirably reduces the rate of the reac tion. Therefore, an intermediate temperature is selected such
that the reaction proceeds at a reasonable rate, but the tem
perature is not so high as to drive the reverse reaction. The

60

version, optimizing heat recovery, reducing utility consump

tion, and recovering residual NH3 and urea from plant e?Iu
ents.

Ammonium nitrate and urea are used as feedstocks in the

65

production of urea-ammonium nitrate (UAN) liquid fertiliz

ers. Most UAN solutions typically contain 28%, 30% or 32%

N, but other customized concentrations (including additional

US 8,398,842 B2
3
nutrients) are produced. The addition of corrosion inhibitors
or the use of corrosion-resistant coatings allows carbon steel

4
chemical cell units must be designed, and control systems for these stacks need to be developed. Recently, attention has been draWn to the removal of CO2 and nitrogen oxides from the environment, as it is conjectured that these compounds contribute to serious problems, includ

to be used for storage and transportation equipment for the

solutions. Continuous and batch-type processes are used, and, in both
processes, concentrated urea and ammonium nitrate solutions

ing the greenhouse effect and acid rain.

The present invention includes electrochemical processes for the production of nitrogen fertilizers including ammo nium nitrate, urea, ammonia, and urea-ammonium nitrate,
using cost-effective sources of carbon and hydrogen or hydrogen equivalent such as carbon monoxide. One embodi ment of the present invention is a loW-temperature and loW pressure electrochemical process for the production of a

are measured, mixed, and then cooled. In the continuous process, the ingredients of the UAN solution are continuously fed to and mixed in a series of appropriately sized static mixers. RaW material ?oW as Well as ?nished product How,

pH, and density are continuously measured and adjusted. The

?nished product is cooled and transferred to a storage tank for
distribution. In the batch process, the raW materials are

sequentially fed to a mixing vessel ?tted With an agitator and

mounted on load cells. The dissolving of the solid raW mate

nitrogen fertilizer Without the need for a hydrogen input.

Another embodiment is an electrochemical process for urea

rial(s) can be enhanced by recirculation and heat exchange as

production using a cost-effective nitrogen source, carbon

sources and a loW-co st hydrogen equivalent rather than high purity hydrogen as required for the Haber and other pro
cesses. Another embodiment is an electrochemical process
20

required. The pH of the UAN product is adjusted prior to the

addition of the corrosion inhibitor.

As described above, the production of high-nitrogen fertil izers involves multi step reactions and is strongly limited by the Haber process. The equilibrium conversion of hydrogen
gas and nitrogen gas to ammonia in the Haber process is generally only on the order of l0%~l5%. Such loW conver

for ammonia production using a cost-effective nitrogen

source and a loW-cost hydrogen equivalent. Another embodi ment is an electrochemical process for the production of urea-ammonium nitrate using cost-effective sources of nitro

sion ef?ciencies give rise to cost-intensive, large-scale chemi cal plants and costly operating conditions required to com mercially produce hundreds to thousands of tons per day of ammonia in an ammonia synthesis plant. Therefore, it is of industrial interest to develop simpli?ed approaches for the production of high-nitrogen fertilizers, especially at small to
middle scales. A one-step process can convert carbon sources,

25

gen and carbon. Another embodiment utilizes greenhouse gases in the electrochemical process for the production of nitrogen fertilizers. The present invention also encompasses electrochemical reactors and reactor components developed speci?cally for the above-described embodiments.
BRIEF SUMMARY

30

nitrogen sources, and/ or hydrogen sources to the high-nitro gen fertilizer at decreased pres sure and/ or temperature has the potential to meet such requirements of small- to middle-scale

production of high-nitrogen fertilizers. Only recently has the feasibility of using electrochemical
processes for urea synthesis been investigated. The most obvious advantages of electrochemical processes over tradi

The present invention encompasses methods and appara tuses for the preparation of nitrogen fertilizers at loW tem perature and/or pressure, preferably at ambient temperature
35

and pressure, utilizing a source of nitrogen, a source of car

bon, a source of hydrogen or hydrogen equivalent, and elec

tional processes mentioned above include (1) simpli?ed pro cess complexity since a one-step process is likely, (2) simpli ?ed operation conditions since electrochemical reaction
could be run even at room temperature and atmospheric pres

tricity. Implementing an electrolyte serving as ionic charge carrier, (1) ammonium nitrate is produced via the reduction of
40

a nitrogen source at the cathode and the oxidation of a nitro gen source at the anode; (2) urea or isomers of urea are

sure, and (3) decreased system volume and size. Several

challenges exist, hoWever, for industrial consideration of the

reported electrochemical process for the preparation of urea. One of these challenges is the high cost of the nitrogen source, as nitrite and nitrate are typically employed. Another of these challenges is the high cost of the hydrogen source, as more hydrogen gas is required because of the use of above-men
tioned nitrite or nitrate compared to the use of a loW-valance nitrogen source such as nitrogen gas or nitric oxide. Commer
45

produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source; (3) ammonia is produced via the hydrogenation of a nitrogen source using a cost-effective

hydrogen or hydrogen equivalent source; and (4) urea-ammo nium nitrate is produced via the simultaneous cathodic reduc
tion of a carbon source and a nitrogen source, and anodic oxidation of a nitrogen source. The source of nitrogen may be a nitrogen-containing com

pound in the electrolyte, a nitrogen-containing gas supplied to

50

the cathode side, or a combination thereof. The source of

cialization of the process is also deterred by the fact that the current ef?ciency for urea formation has been loW and the process has not been optimized. The process involves the reduction of carbon dioxide and nitrogen-containing com

carbon may be a carbon-containing compound in the electro lyte, a carbon-containing gas supplied to the cathode, or a combination thereof. Similarly, the source of hydrogen may
55

pounds. The tWo reactions corresponding to (l) electrochemi cal reduction of CO2 and (2) electrochemical reduction of nitrogen-containing compounds are thermodynamically and
kinetically different. To promote urea formation, the rates of these tWo reactions must be precisely controlled, and this

be hydrogen-containing compound in the electrolyte, a hydro gen- or carbon monoxide-containing gas supplied to the
anode side, or a combination thereof. Accordingly, there are

various combinations of sources for nitrogen and carbon in

combination With one or more sources of hydrogen or hydro

gen equivalent such as carbon monoxide. The electrolyte can

60

requires developing electrocatalysts, selecting electrolytes,

controlling the composition of the reactants and the feeding
rates of the reactants and electrolytes, choosing current or

be aqueous, nonaqueous, or solid.

potential control mode, and implementing temperature con

trol. Additionally, the structures of the electrodes and the electrochemical cells need to be optimized to improve pro cess ef?ciency and decrease process complexity. Finally, for
65

Herein disclosed is a method for producing nitrogen fertil izers selected from the group consisting of ammonium nitrate, urea, ammonia, urea-ammonium nitrate and combi

nations thereof, the method comprising: providing at least

one reactor comprising at least one reaction chamber and at least one anode and at least one cathode; placing at least one electrolyte betWeen each at least one anode and each at least

commercial production, stacks comprising several electro

US 8,398,842 B2
5
one cathode; feeding gaseous or liquid reactants selected from nitrogen sources, carbon sources, hydrogen or hydrogen equivalent sources, and combinations thereof to the reactor; and providing electricity to drive anodic and cathodic reac

6
alkaline and salt, an ionic liquid, or combinations thereof. In embodiments, the reactor comprises at least one solid elec

trolyte selected from the group consisting of polymer elec

trolytes, inorganic solid electrolytes, and combinations

thereof. In some embodiments, the at least one solid electro

tions, thereby producing ammonium nitrate by providing a

nitrogen source to at least one cathode and a nitrogen source to at least anode; urea by providing a carbon source and/or a nitrogen source to at least one cathode, and a hydrogen source

lyte is selected from the group consisting of inorganic proton

conductors, inorganic oxygen-ion conductors, and combina

tions thereof. In embodiments, anodic and cathodic reactions are carried
out at a temperature in the range of from about 0 C. to about 10000 C. In certain embodiments, the electrochemical reac tions are carried out at a temperature in the range of from about 0 C. to about 100 C., and at least one electrolyte is

to at least one anode; ammonia by providing a nitrogen source to at least one cathode, and a hydrogen or hydrogen equiva lent source to at least one anode; urea-ammonium nitrate by
providing a nitrogen source and a carbon source to at least one cathode, and a nitrogen source to at least one anode; or a

combination thereof. The carbon source may be selected from the group consist

liquid electrolyte. In speci?c embodiments, the electrochemi

cal reactions are carried out at a temperature loWer than 2000

ing of carbon dioxide, carbon-containing organic com pounds, carbon-containing gases, and combinations thereof.
In speci?c embodiments, the carbon source is a carbon-con

C. and at least one electrolyte is selected from the group

consisting of solid polymer electrolytes. In alternative

20

taining gas. In embodiments, the carbon-containing gas com

prises carbon dioxide Which may be from an ethanol plant, a fermentation plant, a coal combustion system, a gasi?cation, an adsorption system, a scrubbing system, the Selexol pro cess, the Rectisol process, an amine system, the reforming of
natural gas, or a combination thereof.

embodiments, the electrochemical reactions are carried out at a temperature in the range of from about 2000 C. to about 600 C. and at least one electrolyte is selected from the group

consisting of inorganic proton conductors. In other embodi

ments of the disclosed method, electrochemical reactions are carried out at a temperature greater than a temperature in the range of from 6000 C. to about 10000 C. and at least one
25

The nitrogen source may be selected from the group con

sisting of nitrogen-containing salts, nitrogen-containing

gases, and combinations thereof Wherein the nitrogen-con taining gases include nitrogen oxide With a chemical formula

electrolyte is selected from the group consisting of inorganic oxygen-ion conductors.

In some embodiments, the anodic and cathodic reactions
are carried out at a pressure in the range of from about

NxOy, Where x:l or 2, and y:0, l, 2, 3, 4, 5. In embodiments,

the nitrogen source is a liquid form of nitro gen oxide captured using a solution of metal complexes. In embodiments, the nitrogen oxide comes from a coal combustion plant, a gasi?
cation process, an electric discharge of air process, or a com
30

between 1 atmosphere to about 200 atmospheres.

In some embodiments, feeding at least one gaseous reac tant occurs at a rate of from about 0 SCCM to about 10,000

SCCM. In some embodiments, feeding at least one liquid

reactant or feeding at least one electrolyte occurs at a rate of

bination thereof. The source of hydrogen may be selected from the group

from about 0 mL/min to about 10,000 mL/min.

35

consisting of hydrogen-containing salts, hydrogen-contain

ing compounds, and hydrogen-containing gases. A source of
hydrogen equivalent can be carbon monoxide or a mixture of

In some embodiments of the method, the reactants com prise at least one carbon source and at least one nitrogen source, and the molar ratio of the carbon source to the nitro

carbon monoxide and hydrogen. In embodiments, the hydro

gen source comprises a hydrogen-containing salt selected
40

gen source in the reactants changes from 0.1 to 20 during the electrochemical reaction. At least one anode may comprise at least one catalyst

from the group consisting of ammonium hydroxide (NH4OH) and sodium borohydride (NaBH4). In embodiments, the
hydrogen source comprises a hydrogen-containing gas selected from the group consisting of H2 and NH3. In some embodiments, the hydrogen source comprises a hydrogen
45

selected from the group consisting of precious metals, alloys of precious metals, supported counterparts thereof, and com
binations thereof. At least one cathode may comprise at least one catalyst selected from the group consisting of unsup

containing compound selected from the group consisting of Water, alcohols, and sugars. In embodiments, the hydrogen
source comprises hydrogen gas from the electrolysis of a

ported transition metals, supported transition metals, alloys thereof, organic macromolecular compounds, conductive
polymers, and combinations thereof.
In embodiments, the reactor is an electrochemical reactor. The electrochemical reactor may comprise one chamber that

hydrogen containing compound, Wherein the electrolysis is performed utiliZing electricity from Wind energy, solar
energy, or a combination thereof and the electrolysis of Water

50

contains the reactants, the electrolyte, and the electrodes. Alternatively, the electrochemical reactor may comprise one
gas chamber and one liquid chamber and one porous elec trode or tWo porous electrodes. In still other embodiments, the

takes place in the presence of depolariZers such as coal, sulfur,

and sulfur dioxide to produce hydrogen. In some embodi ments, the hydrogen gas or hydrogen equivalent comes from a coal gasi?cation process, a biomass gasi?cation process, the
reforming of natural gas, or a combination thereof.

55

In embodiments of the method, the at least one electrolyte

is selected from the group consisting of aqueous electrolytes

comprising aqueous solution, nonaqueous electrolytes, and solid electrolytes. In embodiments comprising aqueous elec
trolyte, the aqueous solution may be selected from the group consisting of inorganic acids, alkaline or neutral salts dis
solved in Water, alkaline or neutral salts dissolved in a mixture of Water and at least one organic solvent, and combinations thereof. In embodiments, the reactor comprises at least one

electrochemical reactor may comprise three chambers selected from the group consisting of tWo gas chambers and one liquid chamber, one gas chamber and tWo liquid cham bers, and other combinations of three chambers. In some embodiments, the electrochemical reactor comprises more than three chambers selected from the group consisting of tWo
gas chambers and tWo liquid chambers or tWo gas chambers

60

and three liquid chambers. In embodiments, the electrochemical reactor comprises

one gas chamber and one liquid chamber, and the reactor further comprises at least one gas diffusion electrode separat
65

ing the gas chamber and the liquid chamber.

The electrochemical reactor may comprise no liquid cham
ber and at least one electrolyte selected from the group con

nonaqueous electrolyte selected from the group consisting of organic salt dissolved in an organic solvent, a molten acid,

US 8,398,842 B2
7
sisting of solid electrolytes. In embodiments, a cathode layer
of the cathode, an anode layer of the anode, or both are
porous, and the reactants are gaseous.

8
do not depart from the spirit and scope of the apparatus and
method as set forth in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS

In some embodiments Wherein the reactor comprises three or more chambers, the reactor further comprises a membrane separating the at least one anode and the at least one cathode.

The membrane may be selected from the group consisting of

ion-exchange membranes, porous polymer membranes, inor

ganic porous membranes, and combinations thereof.
In some embodiments, the method comprises at least tWo reactors forming a stack. In these embodiments, the tWo or more reactors may be connected in series, connected in par allel or, in the case of three or more reactors, any combination

For a detailed description of the preferred embodiments of the apparatus and methods of utilizing this apparatus for the production of nitrogen fertilizers, reference Will noW be made to the accompanying draWings in Which:
FIG. 1 schematically shoWs an installation for the electro chemical production of ammonium nitrate from a gaseous nitrogen source, comprising an electrochemical cell Without membrane separator and a reaction tank for the neutralization of excess nitric acid using ammonia according to one embodi ment of the present disclosure. FIG. 2 schematically shoWs an installation for the electro chemical production of ammonium nitrate from gaseous nitrogen source, Which comprises an electrochemical cell With membrane separator and a reaction tank for the neutral ization of excess nitric acid using ammonia according to another embodiment of the present disclosure. FIG. 3 schematically shoWs an installation for the electro chemical production of ammonium nitrate from a liquid nitrogen source, Which comprises an electrochemical cell With membrane separator and a reaction tank for the neutral ization of excess nitric acid using ammonia according to another embodiment of the present disclosure. FIG. 4 schematically shoWs an installation for the electro chemical production of ammonium nitrate from a gaseous

thereof. In embodiments, the at least one electrolyte is liquid, ammonium nitrate is produced, and the method further com prises neutralizing excess nitric acid produced in the reactor by reaction With ammonia in an external neutralization tank. In some embodiments, ammonium nitrate is produced via the reaction of ammonia produced at the cathode and nitric acid produced at the anode outside the reactor. In embodiments, ammonium nitrate is produced, and the at least one electrolyte

20

is liquid electrolyte. In certain embodiments, ammonium

nitrate is produced in the reactor and the at least one electro
25

lyte is solid electrolyte. In embodiments, the method further comprises reacting

ammonia and nitric acid in a reaction tank connected to the reactor. In embodiments, the method further comprises con

verting, in an absorption toWer, oxides of nitrogen With high valance into nitric acid by contacting the oxides With Water. In embodiments, urea is produced and the method com
prises providing a carbon source and a nitrogen source to at

30

nitrogen source and using solid electrolyte, Which comprises

a high-temperature electrochemical cell, a reaction tank for the neutralization of excess nitric acid using ammonia, and an adsorption toWer for the production of nitric acid according to another embodiment of the present disclosure. FIG. 5 schematically shoWs an electrochemical cell With out membrane separator for the production of urea in liquid electrolyte using a gaseous nitrogen source, a gaseous carbon source, and a gaseous hydrogen source, according to another embodiment of the present disclosure. FIG. 6 schematically shoWs an electrochemical cell With membrane separator for the production of urea in liquid elec trolyte using a gaseous nitrogen source, a gaseous carbon source, and a gaseous hydrogen source, according to another embodiment of the present disclosure. FIG. 7 schematically shoWs an electrochemical cell for the production of urea in liquid electrolyte using a gaseous nitro
gen source, a gaseous carbon source, and a liquid hydrogen

least one cathode, feeding a hydrogen or hydrogen equivalent

source to at least one anode, and placing at least one liquid electrolyte betWeen at least one cathode and at least one
35

anode. In alternative embodiments, urea is produced, the at least one electrolyte is solid, and the reactor is a high tem

perature electrochemical cell. In some embodiments, the method further comprises using
a cold trap to capture urea or an isomer of urea.

40

In embodiments, ammonia is produced and the method

comprises providing a nitrogen source to at least one cathode, feeding a hydrogen or hydrogen equivalent source to at least one anode, and placing at least one electrolyte betWeen at
least one cathode and at least one anode.

45

In some embodiments, urea-ammonium nitrate is pro duced, the reactor is an electrochemical cell; the at least one electrolyte is solid; a mixture of urea and ammonia is pro

duced at the at least one cathode; nitrogen dioxide generated

at the at least one anode is converted into nitric acid With Water; and urea, ammonia, and nitric acid are reacted to form

50

source, according to another embodiment of the present dis closure. FIG. 8 schematically shoWs an electrochemical cell for the

production of urea in liquid electrolyte using all liquid forms

of a nitrogen source, a carbon source, and a hydrogen source,

urea-ammonia nitrate. In embodiments, the anodic and cathodic reactions are

according to another embodiment of the present disclosure. FIG. 9 schematically shoWs an installation for the electro

carried out at a constant current mode, a constant potential 55 chemical production of urea from a gaseous nitrogen source

mode, a current-pulse mode, or a potential-scanning mode.

and using dense solid electrolyte, comprising a high-tempera

ture electrochemical cell and a cold trap for the capture of reaction production of urea and/or isomers of urea according to one embodiment of the present disclosure. FIG. 10 schematically shoWs an installation for the elec trochemical production of urea from a gaseous nitrogen

The foregoing has outlined rather broadly the features and technical advantages of the present disclosure in order that the detailed description that folloWs may be better understood. Additional features and advantages of the apparatus and method Will be described hereinafter that form the subject of the claims of this disclosure. It should be appreciated by those skilled in the art that the conception and the speci?c embodi
ments disclosed may be readily utilized as a basis for modi fying or designing other structures for carrying out the same

60

source and using porous solid electrolyte, comprising a high

temperature electrochemical cell and a cold trap for the cap ture of reaction production of urea and/or isomers of urea according to one embodiment of the present disclosure. FIG. 11 schematically shoWs an electrochemical cell for the production of ammonia from a gaseous nitrogen source

65

purposes of the present disclosure. It should also be realized by those skilled in the art that such equivalent constructions

US 8,398,842 B2
9
and a cost effective hydrogen or hydrogen equivalent source

10
anode side may partially or fully offset the energy cost of the

using proton conductive electrolyte, according to another

embodiment of the present disclosure. FIG. 12 schematically shoWs an installation for the elec trochemical production of urea-ammonium nitrate from gas
eous nitrogen source, Which comprises an electrochemical cell With a membrane separator and a reaction tank for the

nitrogen fertilizer production process.

Description of Electrochemical Process In embodiments, nitrogen fertilizers are produced from a
source of nitrogen, a source of carbon, and/or a source of

hydrogen utilizing electrochemical methods.

In one embodiment, ammonium nitrate is produced in aqueous solution at loW temperature and atmospheric pres sure utilizing a single nitrogen source Without the need of hydrogen gas. At the cathode side, a nitrogen source is elec trochemically reduced to ammonia. At the anode side, a nitro gen source is electrochemically oxidized into nitric acid. Reacting ammonia and nitric acid inside or outside of the electrochemical cell results in the formation of ammonium
nitrate. Excess of nitric acid can be neutralized in an addi

neutralization of excess nitric acid using ammonia according to another embodiment of the present disclosure.
The same numbers are used throughout the draWings to refer to the same/ similar components of the apparatus.
DETAILED DESCRIPTION

I. OvervieW
Herein disclosed are an economical apparatus and method

for the production of nitrogen fertilizers. The apparatus com

prises at least one anode and at least one cathode, Wherein reactants selected from nitrogen sources, carbon sources,
20

tional reaction tank With ammonia to generate ammonium nitrate. Both gaseous and liquid nitrogen sources can be used in the electrochemical process of ammonium nitrate. Prefer

ably, the nitrogen source is gaseous nitrogen oxide recovered

from a combustion process of coals, a gasi?cation process of coals or biomass, or their corresponding form captured With

hydrogen or hydrogen equivalent sources and combinations thereof are converted into nitrogen fertilizers. In embodi ments, the apparatus comprises an electrochemical reactor. In embodiments, the electrochemical reactor comprises a gas ?oW ?eld. Alternative embodiments comprise a liquid cham her. In embodiments, the electrochemical reactor comprises at least one cathode, one anode, and one electrolyte component. For improved control and utilization of gaseous sources

liquid absorbents. Typically, employing NO as the nitrogen

source at both anode side and cathode side can produce

ammonium nitrate according to the folloWing reaction:

25

Excess of nitric acid produced at the anode side Will be reacted With added ammonia to form ammonium nitrate.

Alternatively, the liquid form of NO captured by complexes

30

of iron(II) is a suitable nitrogen source used for the formation

involved in the synthesis reaction of nitrogen fertilizers, in embodiments, the electrochemical reactor comprises at least
a gas ?oW ?eld and one gas diffusion electrode. For the

of ammonia at the cathode. Similarly, greenhouse gas nitrous oxide could be used to produce ammonium nitrate as follows:
In Reaction 9, no additional ammonia is required for the

control of liquid components including reactant sources and/ or clcctrolytc Which are involved in the nitrogen fcrtilizcrs synthesis, in embodiments, the electrochemical reactor com prises a liquid chamber to alloW the liquid components to How through the gap betWeen the cathode and anode.

35

production of ammonium nitrate.

In another embodiment, ammonium nitrate can be pro
duced from a nitrogen source in an electrochemical cell based
40

In embodiments, the nitrogen fertilizer production method

herein disclosed is economically desirable compared to con

ventional nitrogen fertilizers production methods. In embodi

ments of the apparatus, the carbon source, the nitrogen
source, the hydrogen or hydrogen equivalent source, or a combination thereof is chosen based on availability and eco

on solid electrolyte, preferably, an oxygen-ion conductor. At the cathode, a nitrogen source may be reduced into ammonia. At the anode, a nitrogen source can be oxidized into the oxides of nitrogen(IV) or (V) Which can be adsorbed With Water to produce nitric acid. Ammonia and nitric acid are then introduced into a reaction tank to produce ammonium nitrate.

nomic advantage. In preferred embodiments, the nitrogen

source comprises nitrogen oxide, and utilization of this nitro gen oxide for the production of nitrogen fertilizers may remove this potentially harmful compound from the environ ment. Reduction of energy consumption and improvement of the current ef?ciency and the selectivity for the nitrogen fertilizers formation are achieved by optimization of the

45

The approach of using solid electrolyte may enable the pro duction of ammonium nitrate of high concentration Without
the need of extensive Water evaporation. In another embodiment, urea is produced from a nitrogen
source, a carbon source and a hydrogen or hydrogen equiva

50

lent source in liquid electrolyte at loW temperature and loW

pressure. A gaseous nitrogen source and a gaseous carbon
source are co-fed at a controlled ratio to the cathode gas

nitrogen fertilizers production process. Optimization of the

process includes any combination of: (l) the use of ef?cient

chamber, While a gaseous hydrogen or hydrogen equivalent

55

electrocatalysts, (2) the selection of suitable electrolytes, (3)

the control of the composition of the reactants and the feeding rates of the reactants and the electrolytes, (4) the selection of current or potential control mode, (5) the implementation of temperature control and (6) the optimization of the structure
of the electrode and the electrochemical reactor. In embodiments, additional economic advantages are real

source is fed to the anode gas chamber. Alternatively, a liquid nitrogen source is used together With a gaseous carbon source and a gaseous hydrogen or hydrogen equivalent source. Pref

erably, greenhouse gases emitted from poWer plants, gasi?

cation processes or ethanol plants are used as a nitrogen source and a carbon source respectively. As an example, nitric
60

ized through the incorporation of a coupled anode process

that provides value-added product thus improving the

economy of the nitrogen fertilizers production process. In embodiments, discussed in more detail herein beloW, the

oxide and carbon dioxide from poWer plants are utilized to produce urea in one step With the addition of hydrogen as folloWs:

anode reactant provides hydrogen-containing or hydrogen equivalent species at the anode-electrolyte interface and is
oxidized to add value to the product. This added value at the

65

In another embodiment related to the production of urea,

solid urea or its isomer can be produced in a solid-state

electrochemical cell based on solid electrolytes. Both nitro

US 8,398,842 B2
11
gen gas recovered from air and other nitrogen sources can be

12
having an inlet 12 and an outlet 13. A liquid electrolyte

used for the high temperature process. The use of nitrogen gas as a nitrogen source requires high reaction temperature, Which is comprised by the stability of urea or its isomer product and the reaction rate. A reaction temperature of 300
6000 C. is preferred at atmospheric pressure. The use of a gaseous nitrogen oxide could alloW the reaction to be oper
ated at temperatures loWer than 350 C. In an electrochemical

prepared by dissolving ion-conductive compounds in Water

or other solvent is contained in the liquid chamber 2 of the vessel and positioned betWeen a cathode 1 and an anode 3. Activation of the electrolytic cell occurs When an electric potential is applied across the electrodes and causes a chemi cal reaction to occur betWeen the ions in solution and the

electrode(s).
In one embodiment shoWn in FIG. 1, the electrolytic cell used for the production of ammonium nitrate at loW tempera
ture and pressure comprises tWo gas chambers, a cathode gas chamber 6 and an anode gas chamber 7, and one liquid elec trolyte chamber 2. Cathode gas chamber 6 has a cathode gas inlet 8 and a cathode gas outlet 10, While anode gas chamber

cell using solid electrolyte, urea may be produced from nitro gen gas in a single step according to the folloWing reaction:
Such a one-step urea process Which can be operated at atmo

spheric pressure has obvious advantages over traditional urea

process requiring tWo high-pressure reactions (Reactions 1 and 6) in terms of process complexity, operating cost, and system complexity. High-purity urea can be produced With
out the need of co stly puri?cation. Similarly, high-purity urea
can be generated using a gaseous nitrogen source through a
reaction such as Reaction 10.
20

In another embodiment, ammonia can be produced in a

solid-state electrochemical cell using a hydrogen equivalent

such as carbon monoxide or a mixture of hydrogen and car

bon monoxide in place of high purity hydrogen. At the anode

side, humidi?ed carbon monoxide (CO) or a humidi?ed mix ture of H2 and CO is fed to the porous anode layer and is
25

7 has corresponding gas inlet 9 and gas outlet 11. Electrolyte chamber 2 has a liquid electrolyte inlet 12 and a liquid elec trolyte outlet 13. At the cathode side, gas diffusion layer 4 provides reactants access to the cathode/electrolyte interface for a cathode reaction; While at the anode side, corresponding anode gas diffusion layer 5 is prepared for the anode reaction of gaseous anode reactants. By the use of selective anode and cathode electrocatalysts, ammonia and nitric acid are pro duced at the cathode and anode, respectively. The ammonia and nitric acid can then react Within the liquid chamber to

produce ammonium nitrate before the liquid phase ?oWs

through a multichannel valve 15. Ammonium nitrate and excess of nitric acid produced in the liquid phase enter a reaction tank 16 Where the excess of nitric acid is neutraliZed into ammonium nitrate using ammonia added through a chan

simultaneously oxidiZed at the anode layer and electrolyte layer interface. At the cathode side, N2 is fed to the porous cathode layer and is electrochemically hydrogenated to yield
ammonia (NH3). Because of the direct use of CO or a
30

nel 17. The liquid phase is cycled back into the liquid chamber
2 through an electrolyte-recycling channel 14 When the con

COiH2 mixture rather than high purity hydrogen, the fertil iZer cost and the process complexity could be signi?cantly
reduced. In yet another embodiment, urea-ammonium nitrate is pro
duced via the cathodic reduction of a nitrogen source and a carbon source to form urea and ammonia and anodic oxida
35

centration of ammonium nitrate is loW in the liquid phase. Ammonium nitrate product could be captured through the

product outlet 19, and remaining liquid phase Will be cycled

through a channel 18 if needed.

tion of a nitrogen source to generate nitric acid. Resulting cathodic products urea and ammonia and anodic product
nitric acid are introduced into a reaction tank to generate the mixture of urea and ammonium nitrate With ammonia neu
40

In another embodiment shoWn in FIG. 2, the electrolytic cell With a membrane separator used for the production of ammonium nitrate at loW temperature and pressure comprises
tWo gas chambers, a cathode gas chamber 6 and an anode gas

chamber 7, and tWo liquid electrolyte chambers: cathode

electrolyte chamber 20 and anode chamber 21, Which are separated by a membrane separator 28. The introduction of the membrane separator could alloW the use of tWo different

traliZing excess nitric acid. In another embodiment related to the production of urea

ammonium nitrate, nitrogen compounds including urea,

ammonia, and the oxides of nitrogen are formed using an electrochemical cell based on solid electrolytes. The oxides of nitrogen such as NO2 and N205 are converted into nitric acid in an absorption toWer using Water. The urea-ammonium nitrate is then produced in a reaction tank by mixing ammo nia, urea, and nitric acid under controlled pH using ammo nium.
45

electrolytes for cathode and anode processes, respectively. Cathode electrolyte chamber 20 has a liquid electrolyte inlet 22 and a liquid electrolyte outlet 24, and anode electrolyte chamber 21 has a liquid electrolyte inlet 23 and a liquid electrolyte outlet 25. In the membrane electrochemical cell, ammonia is produced at the cathode, and nitric acid is pro
duced at the anode. There is no neutralization of ammonia and nitric acid in the electrochemical cell. All neutralization
occurs inside the reaction tank 16 With the addition of ammo

50

Description of the Process Installation In order to describe the apparatus and method of the present disclosure, reference Will noW be made to FIGS. 1 through 12, Which depict various con?gurations that may be selected depending on Which nitrogen fertiliZer is produced and What
feedstocks are used. The apparatus and methods herein dis closed are not, hoWever, limited to the embodiments of FIGS.

nia. Cathode electrolyte phase and anode electrolyte phase

55

are cycled back into the electrochemical cell through a cath ode electrolyte channel 26 and an anode electrolyte channel

27, respectively.
In the embodiment shoWn in FIG. 3, the use of a liquid nitrogen source at the cathode side for the production of
60

1 through 12. The nitrogen fertiliZers production method of the present disclosure comprises providing an electrolyte
positioned betWeen cathode 1 and anode 3, providing a source
of carbon, a source of nitrogen, and/ or a source of hydrogen or

hydrogen equivalent from Which hydrogen-containing spe

cies are formed, and providing a source of electricity to drive

ammonium nitrate is used to obviate the need of a cathode gas chamber 6 With inlet 8 and outlet 10 and a gas diffusion layer 4. In an embodiment shoWn in FIG. 4, an electrochemical cell

reaction(s) at the electrode(s) Whereby the nitrogen fertiliZers

are produced.
65

based on solid electrolyte eliminates the liquid chamber for the production of ammonium nitrate. Solid oxygen-ion con
ductor 31 simultaneously serves as current carrier and sepa

Generally, electrolytic cells Without a membrane separator comprise a vessel in Which electrolysis takes place, the vessel

rator. Ammonia is produced at the cathode side, and unre

acted reactants are fed back to the cathode gas chamber 6