# Patent

## Title
Ammonia recovery device and recovery method

## Abstract

A method includes a first step of, with a CO2.H2S stripper maintained to have a pressure higher than atmospheric pressure, from the ammonia-containing wastewater, discharging CO2 and H2S in a form of gas having a low moisture concentration from a tower top of the CO2.H2S stripper while discharging an ammonia-containing solution from a tower bottom of the CO2.H2S stripper; a second step of introducing the ammonia-containing solution obtained after the first step into an ammonia stripper which is maintained to have a lower pressure than that of the CO2.H2S stripper, and thereby discharging a gas rich in ammonia containing a small amount of H2S and CO2 from a tower top of the ammonia stripper while discharging water usable as industrial water from a tower bottom of the ammonia stripper; and a third step of introducing the ammonia rich gas obtained after the second step into a washing tower which is maintained to have a lower pressure than that of the ammonia stripper, and thereby discharging a wastewater containing a Na compound from a tower bottom of the washing tower while discharging a H2S-free gas rich in ammonia from a tower top of the washing tower.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a divisional of U.S. application Ser. No. 12/907,516 filed Oct. 19, 2010, which claims priority to Japanese application No. JP2009-243169, filed Oct. 22, 2009. The contents of these applications are hereby incorporated by reference in their entirety.


BACKGROUND OF THE INVENTION
The present invention relates to an ammonia recovery device and to a recovery method, with which ammonia is recovered together with CO2 and H2S from an ammonia-containing wastewater from a gasification furnace, such as a coal gasification furnace, using a fossil fuel as a raw material, whereby the purified wastewater is usable as industrial water.
Wastewaters from gasification furnaces, such as coal gasification furnaces, which use a fossil fuel as a raw material, contain ammonia (NH3) as well as CO2, H2S, and the like. Accordingly, in general, an ammonia stripper is operated under atmospheric pressure to release NH3, CO2, and H2S contained in the wastewaters while water that is reusable as industrial water is recovered from a tower bottom of the ammonia stripper.
H form of a conventional device for recovering ammonia from such a wastewater as described above is shown in FIG. 3. In FIG. 3, an ammonia stripper 301 is operated under atmospheric pressure, and an ammonia-containing wastewater (also containing CO2 and H2S) is introduced through a wastewater supply pipe 302 into this ammonia stripper 301.
The ammonia stripper 301 is maintained at a pressure, measured by a pressure gauge 303, of atmospheric pressure and at a temperature, measured by a thermometer 304, of approximately 90° C. In this case, NH3, CO2, H2S, and water (H2O) are released from the ammonia-containing wastewater; therefore, NH3, H2S, and CO2 gases are discharged from a tower top 305. These NH3, H2S, and CO2 gases are to be served for burning. Furthermore, a wastewater from a tower bottom 306 of the ammonia stripper 301 is used as industrial water.
It should be noted that the NH3 and H2S gases change as follows:

NH3→N2+H2O

H2S→SO2+H2O

Furthermore, in FIG. 4, another form of a conventional device for recovering ammonia from a wastewater is shown. Note that this form is suggested in the paragraph [0003] of JP 2004-67849 A.
In FIG. 4, an ammonia stripper 401 is generally operated under normal pressure (atmospheric pressure), and an ammonia-containing wastewater (also containing CO2 and H2S) is introduced through a wastewater supply pipe 402 into the ammonia stripper 401. At this time, NaOH is supplied to the wastewater supply pipe 402 from a NaOH supply pipe 407 so that NaOH can be injected into the ammonia-containing wastewater.
The ammonia stripper 401 is maintained at a pressure, measured by a pressure gauge 403, of normal pressure (atmospheric pressure) and a temperature, measured by a thermometer 404, of approximately 90° C. In this case, NH3 and water (H2O) are released from the ammonia-containing wastewater containing NaOH; therefore, NH3 and water (H2O) are discharged from a tower top 405 in the form of an ammonia vapor product.
With the supply of NaOH, the following reactions occur.

NaOH+H2S→NaSH+H2O

2NaOH+CO2→Na2CO3+H2O

As a result, NaOH, Na2CO3, NaSH, and water (H2O) are discharged from a tower bottom 406, and then transferred for wastewater treatment.
However, the above-described techniques both have their own drawbacks as follows.
The device for recovering ammonia from a wastewater shown in FIG. 3 has the following problems.
(1) NH3 together with CO2, H2S, water (H2O), and the like discharged from the tower top 305 of the ammonia stripper 301 are burned in an incinerator, and then subjected to flue gas desulfurization. Accordingly, ammonia (NH3) cannot be recovered.
(2) In addition, for the purposes of efficiently releasing ammonia and preventing precipitation of ammonium carbonate, the outlet temperature (the thermometer 304) of the ammonia stripper 301 needs to be maintained at approximately 90° C. This results in an increase in the amount of moisture contained in the gas. Accordingly, although sulfur can be recovered in the form of gypsum during the desulfurization, there arise problems in that the cost increases or in that only dilute sulfuric acid can be recovered, since water separation is essential for a gas used as a raw material gas for production of highly concentrated sulfuric acid (98 wt %).
In addition, the form of the device for recovering ammonia from a wastewater as shown in FIG. 4 has the following problems.
(1) In order to recover ammonia, it is possible to recover a gas rich in NH3 from the tower top 405 by supplying NaOH through the NaOH supply pipe 407 to be mixed into an ammonia-containing wastewater so as to fix CO2 and H2S by the action of NaOH. However, in such a case, the amount of NaOH to be used is enormous (for example, at a commercial scale of 1000-fold expansion of the laboratory base shown in Table 1, it would be approximately 35 tons per day).
(2) In addition, without the supply of NaOH, water with a quality approximately equivalent to that of industrial water can be obtained from the tower bottom 406 of the ammonia stripper 401. However, when NaOH is added to this water, such a quality that is approximately equivalent to that of industrial water cannot be maintained. Accordingly, thus obtained water needs to be sent to a wastewater treatment facility for treatment to restore a quality approximately equivalent to that of industrial water.
SUMMARY OF THE INVENTION
The present invention has been made in view of the above-described problems in the conventional art. An object of the present invention is to provide a device and a method for recovering ammonia from a wastewater, which are capable of obtaining: a H2S-free ammonia-steam mixture gas having a concentration of 90 wt % or above; water reusable as industrial water; and a CO2.H2S rich gas suitable even for production of sulfuric acid.
In order to achieve the above object, an aspect of the present invention provides an ammonia recovery method for recovering ammonia from an ammonia-containing wastewater from a gasification furnace. The ammonia recovery method includes: a first step of, with a CO2.H2S stripper maintained to have a pressure higher than atmospheric pressure, from the ammonia-containing wastewater, discharging CO2 and H2S in a form of gas having a low moisture concentration from a tower top of the CO2.H2S stripper while discharging an ammonia-containing solution from a tower bottom of the CO2.H2S stripper; a second step of introducing the ammonia-containing solution obtained after the first step into an ammonia stripper which is maintained to have a lower pressure than that of the CO2.H2S stripper, and thereby discharging a gas rich in ammonia containing a small amount of H2S and CO2 from a tower top of the ammonia stripper while discharging water usable as industrial water from a tower bottom of the ammonia stripper; and a third step of introducing the ammonia rich gas obtained after the second step into a washing tower which is maintained to have a lower pressure than that of the ammonia stripper, and thereby discharging a wastewater containing a Na compound from a tower bottom of the washing tower while discharging a H2S-free gas rich in ammonia from a tower top of the washing tower.
Here, the washing tower may include a water washing tower located above and a NaOH washing tower located below which are coupled to each other. Moreover, the third step may include: a NaOH washing step in which the gas rich in ammonia obtained after the second step is introduced into the NaOH washing tower so as to absorb H2S and CO2 with NaOH contained in a circulation water in the NaOH washing tower and to then send a resultant gas to the water washing tower while discharging a wastewater containing a Na compound from a tower bottom of the NaOH washing tower; and a water washing step in which a make-up water is supplied to the H2S-free gas rich in ammonia subjected to the washing in the NaOH washing step so as to wash dispersion of droplets of NaOH with the make-up water, the water washing step being carried out in the water washing tower maintained to have a lower pressure than that of the ammonia stripper.
Additionally, the wastewater containing a Na compound from the tower bottom of the NaOH washing tower may be injected into a wastewater passage of a scrubber located downstream of the gasification furnace for neutralization.
Furthermore, another aspect of the present invention provides an ammonia recovery device which recovers ammonia from an ammonia-containing wastewater from a gasification furnace. The ammonia recovery device includes: a CO2.H2S stripper which has an inner pressure maintained to be higher than atmospheric pressure; an ammonia stripper which has an inner pressure maintained to be lower than that of the CO2.H2S stripper; and a washing tower which has an inner pressure maintained to be lower than that of the ammonia stripper. The CO2.H2S stripper has: a tower top from which CO2 and H2S are discharged in a form of a gas having a low moisture concentration from the ammonia-containing wastewater; and a tower bottom from which a solution containing ammonia is discharged. The ammonia stripper has: a tower top from which a gas rich in ammonia is discharged from the solution containing ammonia discharged from the CO2.H2S stripper; and a tower bottom from which a water reusable as industrial water is discharged. The washing tower has: a tower bottom from which a wastewater containing a Na compound is discharged; and a tower top from which a H2S-free gas rich in ammonia is discharged.
Here, the washing tower may include a water washing tower located above and a NaOH washing tower located below which are coupled to each other. The NaOH washing tower has: a connecting part through which the gas rich in ammonia from the ammonia stripper is sent to the water washing tower located above the NaOH washing tower after H2S and CO2 are absorbed with NaOH in a circulating water containing NaOH; and the tower bottom from which the wastewater containing a Na compound is discharged. The water washing tower has a tower top from which the gas rich in ammonia is discharged after a make-up water is supplied to the gas rich in ammonia sent through the connecting part of the NaOH washing tower so as to wash dispersion of droplets of NaOH with the make-up water.
The present invention provides a device and a method for recovering ammonia from an ammonia-containing wastewater, which are capable of obtaining: a H2S-free ammonia-steam mixture gas having a concentration of 90 wt % or above; water reusable as industrial water; and a CO2.H2S rich gas suitable even for production of sulfuric acid.



BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a system diagram describing a device for recovering ammonia from an ammonia-containing wastewater according to an embodiment of the present invention.
FIG. 2 is a system diagram describing an embodiment of a system to which the device for recovering ammonia from an ammonia-containing wastewater according to the present invention is applied.
FIG. 3 is a system diagram of a main part of an ammonia recovery device according to a conventional art.
FIG. 4 is a system diagram of a main part of an ammonia recovery device according to another conventional art.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Hereinafter, an ammonia recovery device and a recovery method according to the present invention will be described in detail by referring to an embodiment shown in the attached drawings.
FIG. 1 shows an embodiment of the ammonia recovery device according to the present invention.
In the embodiment shown in FIG. 1, the main constituents of the device for recovering ammonia from a wastewater are a CO2.H2S stripper 10, an ammonia stripper 20, and a washing tower 30 having therein a NaOH washing tower 31 and a water washing tower 32 which are vertically coupled to each other.
The inner pressure of the CO2.H2S stripper 10 is maintained to be higher than atmospheric pressure. Specifically, the inner pressure of the CO2.H2S stripper 10 is maintained in a range from 2 to 4 kg/cm2G.
In addition, the inner pressure of the ammonia stripper 20 is maintained to be lower than that of the CO2.H2S stripper 10. Specifically, the inner pressure of the ammonia stripper 20 is maintained to be lower than that of the CO2.H2S stripper 10 and to be in a range from 0.5 to 2 kg/cm2G.
Furthermore, the inner pressure of the washing tower 30 is maintained to be lower than that of the ammonia stripper 20. Specifically, the inner pressure of the washing tower 30 is maintained to be lower than that of the ammonia stripper 20 and to be in a range from 0 to 1.5 kg/cm2G.
An ammonia-containing wastewater St•1 which contains ammonia (NH3) is introduced into the CO2.H2S stripper 10 through an ammonia-containing wastewater pipe 11. The ammonia-containing wastewater St•1 is introduced via a steam heater 12 for heating of inlet wastewater.
At an upper portion of the CO2.H2S stripper 10, a pressure gauge 13 which measures the inner pressure of the CO2.H2S stripper 10, and a thermometer 14 which measures the inner temperature thereof, are provided.
A CO2.H2S rich gas St•2 having been discharged from a tower top 15 of the CO2.H2S stripper 10 is discharged to an incinerator or the like (details will be described later).
Furthermore, the CO2.H2S stripper 10 has a pump 16 for circulation of a liquid inside the CO2.H2S stripper 10. The liquid in the CO2.H2S stripper 10 circulates inside the CO2.H2S stripper 10 upwardly and downwardly by the action of the pump 16.
Furthermore, the CO2.H2S stripper 10 has a steam heater 18 for heating of liquid in a tower bottom 17 of the CO2.H2S stripper 10. The liquid heated by the steam heater 18 is returned to the CO2.H2S stripper 10 after the heating.
Note that, in the middle of the CO2.H2S stripper 10, a dam 19 for storage of liquid is disposed.
A solution St•3 from the tower bottom 17 of the CO2.H2S stripper 10 is introduced into the ammonia stripper 20. At an upper portion of the ammonia stripper 20, a pressure gauge 21 and a thermometer 22 which are similar to those of the CO2.H2S stripper 10 are provided.
Furthermore, the ammonia stripper 20 has a pump 23 for circulation of a liquid inside the ammonia stripper 20. The liquid inside the ammonia stripper 20 circulates inside the ammonia stripper 20 upwardly and downwardly by the action of the pump 23.
Furthermore, the ammonia stripper 20 has a steam heater 25 for heating of liquid in a tower bottom 24 of the ammonia stripper 20. The liquid heated by the steam heater 25 is returned to the ammonia stripper 20 after the heating.
Note that, in the middle portion of the ammonia stripper 20, a dam 27 for storage of liquid is disposed.
A gas from a tower top 26 of the ammonia stripper 20, that is, an ammonia-rich gas St•4 containing a small amount of CO2 and H2S is introduced into the NaOH washing tower 31 of the washing tower 30.
Then, a water St•5 from the tower bottom 24 of the ammonia stripper 20 is discharged as industrial water through a steam heater 28 and a pump 29.
The washing tower 30 is integrally formed, as described above, with the NaOH washing tower 31 located below and the water washing tower 32 located above, which are vertically coupled to each other. An upper portion of the NaOH washing tower 31 communicates with the water washing tower 32 through a communicating opening 33. Note that the communicating opening 33 is formed into the shape of a dam, and forms a connecting part.
The ammonia-rich gas St•4, which contains a small amount of CO2 and H2S, from the tower top 26 of the ammonia stripper 20 is introduced into a lower portion of the NaOH washing tower 31 of the washing tower 30.
A solution from a tower bottom 34 circulates through a circulation pipe 36 by the action of a pump 35 and flows into the NaOH washing tower 31 of the washing tower 30. Along the circulation pipe 36, an injection pipe 37 for injection of a NaOH (sodium hydroxide) St•8 is connected so that NaOH can be injected into the NaOH washing tower 31 through the injection pipe 37.
Furthermore, the tower bottom 34 of the NaOH washing tower 31 also discharges a wastewater St•7 to a wastewater treatment facility through the pump 35.
Furthermore, the water washing tower 32 of the washing tower 30 described above has a circulation pipe 39 which connects the lower portion of the water washing tower 32 to the upper portion thereof so as to circulate liquid by the action of a pump 38. A make-up water pipe 40 which feeds a make-up water to the circulation pipe 39 as necessary is provided to feed a make-up water St•9 to the water washing tower 32.
A H2S-free ammonia vapor St•6 as a product from a tower top 41 of the washing tower 30 is supplied to a desired destination to be used.
Note that coolers 45 provided downstream of the pumps 16, 23, 29, 35, and 38 are air-cooling type coolers (air coolers), but may be cooling-water type heat exchangers.
Here, Table 1 shows an example of the compositions of the fluids denoted by St•1 to St•9 when the embodiment in FIG. 1 is carried out. Note that the fluids denoted by St•1 and the like, respectively, are denoted as Stream No. 1 and the like in Table 1.

















TABLE 1







Stream
Stream
Stream
Stream
Stream
Stream
Stream
Stream
Stream



No. 1
No. 2
No. 3
No. 4
No. 5
No. 6
No. 7
No. 8
No. 9

























H2O (g/hr)
26,432.50
5
26,427.50
108.7
26,318.80
16.2
112.5
10
10


H2S (g/hr)
9.6
8.1
1.5
1.5
0
0
1.5
0
0


CO2 (g/hr)
435.8
431.6
4.2
4.1
0.1
0
4.1
0
0


NH3 (g/hr)
222.1
5.1
217
216.3
0.7
216.3
0
0
0


NaOH (g/hr)
0
0
0
0
0
0
10
10
0


Total (g/hr)
27,100.00
449.8
26,650.20
330.6
26,319.60
232.5
128.1
20
10


Temperature
63
55
141
90
124
55
50
30
30


(° C.)


Pressure
5
2.8
3.1
1
1.3
0.5
0.8
0.6
0.5


(kg/cm2G)









Next, the operation of the ammonia recovery device described by referring to FIG. 1 will be described.
In FIG. 1, the ammonia-containing wastewater St•1 which contains ammonia (NH3) is introduced into the CO2.H2S stripper 10 through the ammonia-containing wastewater pipe 11 as described above.
The CO2.H2S stripper 10 is operated while the inner pressure of the CO2.H2S stripper 10 measured by the pressure gauge 13 is maintained at, for example, approximately 3 kg/cm2G, which is higher than atmospheric pressure, and the inner temperature of the CO2.H2S stripper 10 measured by the thermometer 14 is, for example, as low as approximately 55° C.
For this reason, with the above-described conditions of the inner pressure and the inner temperature, scattering of ammonia (NH3) from the tower top 15 of the CO2.H2S stripper 10 is prevented; the CO2.H2S rich gas St•2 can maintain the concentration of the sum of CO2 and H2S to be 90 wt % or above (Table 1) and a low moisture concentration (Table 1, the amount of H2O is 5 g/h or lower); therefore, a CO2.H2S rich gas which contains a lesser amount of ammonia and steam can be extracted.
Thus, a tower top gas having a low moisture concentration as described above can be widely applied to gypsum recovery or sulfur recovery of an incinerator or as a raw material gas for production of sulfuric acid.
Furthermore, the tower bottom solution St•3 from the tower bottom 17 of the CO2.H2S stripper 10 is rich in H2O and NH3 (ammonia) (Table 1). This gas St•3 rich in H2O and NH3 is introduced into a middle portion of the ammonia stripper 20.
The inner pressure of the ammonia stripper 20 measured by the pressure gauge 21 is maintained to be lower (normal pressure) than the pressure of the CO2.H2S stripper 10, and the inner temperature of the ammonia stripper 20 measured by the thermometer 22 is maintained to be high (for example, approximately 90° C.).
Accordingly, the tower top gas St•4 discharged from the tower top 26 of the ammonia stripper 20 becomes rich in ammonia but contains a small amount of CO2 and H2S (Table 1, NH3.H2O.H2S gas). The tower top gas St•4 is then sent to the NaOH washing tower 31 of the washing tower 30.
Meanwhile, the water St•5 (Table 1) which is reusable as clean industrial water is obtained from the tower bottom 24 of the ammonia stripper 20.
The tower top gas St•4 containing ammonia from which CO2 and H2S have been released is an ammonia rich gas (NH3.H2O.H2S gas) containing a small amount of CO2 and H2S as described above.
In the NaOH washing tower 31, NaOH is injected into this ammonia rich gas, that is, the circulating water St•8 (Table 1) containing NaOH is injected into the circulation pipe 36. The temperature and the pressure of the circulating water St•8 to be injected are approximately 0.6 kg/cm2G at 30° C.
As a result, NaOH in the circulating water St•8 absorbs only the remaining CO2 and H2S; thus, the amount of NaOH used can be greatly reduced. For example, the amount, which is 35 tons per day in the device of the conventional art shown in FIG. 4, can be reduced to 5 tons per day in the present invention.
The gas from which the remaining CO2 and H2S have been absorbed by NaOH in the NaOH washing tower 31 is an ammonia vapor containing a small amount of steam. With this gas flowing into the water washing tower 32 located immediately above the NaOH washing tower 31, a water washing process is performed in which the make-up water St•9 is supplied through the make-up water pipe 40 into the water washing tower 32 so that dispersion of droplets of NaOH can be washed off. The temperature and the pressure of the make-up water St•9 to be injected are approximately 0.5 kg/cm2G at 30° C.
Furthermore, the tower bottom 34 of the washing tower 30 communicates with a wastewater treatment facility through the pump 35. The wastewater St•7 (Table 1) is a water containing a sodium compound, such as Na2CO3 and NaSH.
As a result, the gas St•6 (Table 1) discharged from the tower top 41 of the washing tower 30 is a H2S-free gas rich in ammonia, and thereby preferably used as an ammonia vapor product.
FIG. 2 shows one form of a preceding system which generates an ammonia-containing wastewater to be treated by the ammonia recovery device according to the present invention.
As shown in FIG. 2, a gasified gas generated in a coal gasification device 57 is thermally recovered in thermal recovery devices 58 and 59. Between these thermal recovery devices 58 and 59, a scrubber 55 is disposed. Thermally recovered gas (made of CO2, CO, H2, N2, NH3, H2S, and the like) is introduced into a gas cooling tower 51.
The gas subjected to a cooling treatment in the gas cooling tower 51 is introduced into a gas washing tower 52 to be subjected to a washing treatment, and then introduced into a gas turbine through a H2S absorbing tower 60.
In the meantime, wastewaters from tower bottom portions of the gas cooling tower 51 and the gas washing tower 52 circulate by the actions of pumps 53 and 54, respectively. Then, a certain amount of the wastewater is sent as an ammonia-containing wastewater to the CO2.H2S stripper 10 described in FIG. 1.
In this case, the wastewater St•7 from the tower bottom 34 of the washing tower 30 can be supplied to a wastewater passage 56 of the scrubber 55. In this way, it is possible to neutralize a harmful acidic constituent (chlorine, F, or the like) included in the scrubber 55 with the above-described Na compound remaining in the wastewater St•7.
Hereinabove, an embodiment of the present invention has been described; however, the present invention is not limited to the described embodiment, and various changes and modifications are possible based on the technical concepts of the present invention.
The disclosure of Japanese Application No. 2009-243169 filed on Oct. 22, 2010 including specification, claims, drawings and abstract thereof is incorporated herein by reference in its entirety.

## Claims

1. An ammonia recovery device for recovering ammonia from an ammonia-containing wastewater from a gasification furnace, the ammonia recovery device comprising:
a CO2.H2S stripper configured for maintaining an inner pressure higher than atmospheric pressure;
an ammonia stripper configured for maintaining an inner pressure lower than that of the CO2.H2S stripper; and
a washing tower configured for maintaining an inner pressure maintained lower than that of the ammonia stripper; wherein
the CO2.H2S stripper has:
a tower top portion configured for the discharge of CO2 and H2S gas; and
a tower bottom portion configured for the discharge of a solution containing ammonia;

the ammonia stripper has:
a tower top portion configured for the discharge of a gas rich in ammonia;
a connection to the tower bottom portion of the CO2.H2S stripper configured for introducing the solution containing ammonia discharged from the CO2.H2S stripper; and
a tower bottom portion configured for discharging a water reusable as industrial water; and

the washing tower includes:
a water washing tower located above; and
a NaOH washing tower located below which are coupled to each other, the NaOH washing tower has:
a connection to the tower top portion of the ammonia stripper configured for introducing a gas rich in ammonia discharged from the ammonia stripper;
a connecting part to the water washing tower located above the NaOH washing tower configured for sending the gas rich in ammonia after treatment with NaOH in a circulating water to absorb H2S and CO2;
a tower bottom portion configured for the discharge of a wastewater containing a Na compound;
a circulation pipe configured for the circulation of a solution from the tower bottom back into the NaOH washing tower by the action of a pump; and
an injection pipe connected to the circulation pipe configured for the injection of NaOH into the NaOH washing tower through the injection pipe, and

the water washing tower has a tower top portion configured for the discharge of a purified gas rich in ammonia after a make-up water is supplied to the gas rich in ammonia sent through the connecting part of the NaOH washing tower so as to wash with the make-up water.