CA2024087A1 - Process for the reduction of the emission of noxious materials in combustion processes - Google Patents
Process for the reduction of the emission of noxious materials in combustion processesInfo
- Publication number
- CA2024087A1 CA2024087A1 CA 2024087 CA2024087A CA2024087A1 CA 2024087 A1 CA2024087 A1 CA 2024087A1 CA 2024087 CA2024087 CA 2024087 CA 2024087 A CA2024087 A CA 2024087A CA 2024087 A1 CA2024087 A1 CA 2024087A1
- Authority
- CA
- Canada
- Prior art keywords
- process according
- sprayed
- aqueous solution
- cyanamide
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
Abstract Process for the reduction of the emission of noxious materials in combustion processes The present invention provides a process for the reduction of noxious materials in combustion processes, wherein an aqueous solution of cyanamide and/or hydrogen cyanamide is sprayed in finely-dispersed form into the combustion chamber. In this way, with low technical expense, even in the case of combustion processes with greatly varying emissions of noxious materials, a degree of removal of nitrogen of > 90 is achieved.
Description
2~8~
The present invention is concerned with a process for reducing the emission of no~ious materials in the case of combustion processes and especially for lowering emissions of oxides of nitrogen.
It is known that the em$ssions of noxious materials resulting from the combustion of fossil energy carriers and of garbage can b~ considerably reduced by the addition of appropriate additives.
In the case of the removal of nitrogen from flue gases, besides the catalytic processes, which, however, give rise to technical problems because of the large spatial requirements of the catalyst masses, non-catalytic processes have also bean developed in which, in particular, the use of ammonia has found use i~
the technology because of its selective ~ction.
Disadvantages in the case of the use of ammonia include the diffiaulty of handling it and the special safety measuras necessary whlch make necessary a large technical expenditure.
Published Federal Republic of Germany Patent Specification No. 29 26 107 descrlbes a process for the removal of oxides o nitrogen, as well as possibly of halogens, sulphur and/or halogen compounds from gases, in which the gases are passed in the presence of water at temperatures below 80C. over a cyanamide or through a solution or suspension of a cyanamide and the noxious materials are separated off. However, because of the high costs of the apparatus, this 2~2~
process has not proved useful in the technology.
In the case of the process described in published Federal Republic of Germany Patent Specification No.
34 47 616, as additive for the simultaneous removal of the oxides of sulphur and nitrogen from waste gases, it is recommended to use finely-ground agents based on calcium compounds with a content of 1 to 90~ by weight of calcium cyanamide and especially of nitrogenated lime. Quite apart from the fact that the additive must be blown in in finely dispersed orm, which makes necessary a laborious grinding procedure, these dry additives based on nitrogenated lime zre comparatively inert. This has a negative effect especially in the case of those gas purification processes in which a relative high speed of reaction is necessary.
In World Intellectual Property Organisation's Patent Specification WO 87/02023, there is described a process for the reduction of emissions of oxides of nitrogen in which, besides a series of guanidine and urea compounds, calcium cyanamide is also sprayed into waste gases in the form of a solution at a temperature o~ about 1100 to 1370C. It is a disadvantage of this prscess that stable solutions of calcium cyanamide can only be produced with relative difficulty and that, in this way, only moderate rates of nitrogen removal can be achieved which are at a maximum of only about 50%.
` - 2~2~8~
Therefore, the present invention seeks to provide a process for the reduc~ion of emissions of noxious materials which does not display tha mentloned disadvantages o-f the prior art but rather makes possible an effective reduction especially of oxides of nitrogen with a low technical expense.
Thus, according to the present invention, there is provided a process for reducing the emission of noxious materials in the case of combustion processes, wherein an aqueous solution of cyanamide and/or of a hydrogen cyanamide salt is sprayed in finely-dispersed form into the combustion chamber.
Surprisingly, it has now been found that, in this way, a substantially better reduction of the values of the oxides of nitrogan can be achieved than in the case of the known processes based on the use of calcium cyanamide as additive.
In the case of the process according to the present invention, as additiYe there is used an aqueous solution of cyanamide and/or hydrogen cyanamide salts, in which case, a~ hydrogen cyanamide salts, the alkali metal and alkaline earth metal salts are to be regarded as being especially preferred because of their inexpensive availability.
As alkali metal salts, sodium and potassium hydrogen cyanamide are hereby espPcially preferred, which are obtainable from cyanamide according to known processes .
~2~
In the case of the alkaline earth metal salts, calcium and magnesium hydrogen cyanamide are especially preferably used.
According to a preferred embodiment of the process according to the presant invention, calcium dihydrogen cyanamide (Ca(HCNz )2 ) iS used which can be produced especially simply from a technical suspension of nitrogenated lime by separating the supernatant solution from insoluble residue, for example by decantation or filtration. This clsar solution, which essentially contains calcium dihydrogen cyanamide, can be used directly in the process according to the present invention without further purification.
The concéntration of the aqueous solution of cyanamide and/or hydrogen cyanamide can be varied within wide limits but, for economic reasons, it has proved to be advantageous to adjust the concentration to 5 to 50~ by weight, referred to the cyanamide content.
The aqueous solutions used according to the present invention can also contain conventional stabilizers, ~or example magnesium salts, according to published Federal Republic of Germany Patent Specification No.
32 19 054 or carboxylic acid esters according to published Federal Republic of Germany Patent Specification No. 26 42 043, which improve the storage stability of the solutions.
2~2~
It is important for the present invention that the aqueous treatment solutions are sprayed in finely dispersed form into the combustion chamber as uniformly as possible, which can be achieved without problems with the use of conventional technical means, for example nozzles. In this way, there results an optimum rate of reaction or reduction of noxious materials. The aqueous solutions can also be sprayed in with the help of carrier gases, for example the combustion air, saturated steam or other gases which behave in an inert manner and do not enter into any undesired side reactions. Preferably the aqueous solutions of cyanamide and/or hydrogen cyanamide salts are sprayed in at a pressure of from 1 to 10 bar in such a way that the droplets have a particle size of < 100 ~m.
The process according to the present invention can be used in a wide temperature range, temperatures of 300 to 1100C. and especially of 600 to 1000C.
being preferred.
The amount of additive necessary for the reduction of the emission of noxious materials depends essentially on the concentrations of noxious materials in the combustible material and can, consequently, vary in wide limits. In the case of usual combustion plants, such as garbage incineration plants and power stations, which, according to capacity, combustible material and 2~24D87 operating conditions relating to an emission of oxides of nitrogen in amounts of from 200 to 1300 mg./Nm3, normally 1 to 20 kg. of cyanamide per 1000 Nm3 of waste gas are necessary in order to achieve a degree of removal of nitrogen of > 90%. At the same time, however, there also takes place a marked reduction o other noxious materials, such as sulphur dioxide, halogens and halogenated hydrocarbons. Because of this good reduction of the amounts of noxious ma-terials, of the cost-favourable additives, as well as of the low technical expense, the process according to the present invention is outstandingly useful for use on a large scale, especially in the case of combustion processes with greatly varying emissions of noxious materials.
The ollowing Examples are given for the purposP
of illustrating the present invention:
Example 1.
In a garbage incineration plant for domestic and industrial waste, in the case of the incineration of 9 tonnes of garbage per hour, there are produced about 60,000 Nm3/hour of waste gas with an average content of oxides of nitrogen of 480 mg./Nm3 and an average oxygen content of 11%.
A 25% aqueous solution of calcium dihydrogen cyanamide (produced by mixing 637 g. of nitrogenated lime and 880 g. water, followed by separation of the supernatant solution) was sprayed with carrier 8 ~
air and atomizer air into the combus~ion chamber in an amount of 350 kg./hour ~particle size of the droplets < 25 ~m.). The content of oxides of nitrogen in the waste gas was reduced to 40 mg./Nm3, which corresponds to a degree of nitrogen removal of about 92%.
Example 2.
In the same combustion process as described in Example 1, 350 kg./hour of a 25~ aqueous cyanamide solution were sprayed into the combustion chamber with carrier air and atomizer air (particle size of the droplets ~ 25 ~m.). The content of oxides of nitrogen in the waste gas was reduced to 50 mg./Nm3, which corresponds to a degree of removal of nitrogen of about 90~.
The present invention is concerned with a process for reducing the emission of no~ious materials in the case of combustion processes and especially for lowering emissions of oxides of nitrogen.
It is known that the em$ssions of noxious materials resulting from the combustion of fossil energy carriers and of garbage can b~ considerably reduced by the addition of appropriate additives.
In the case of the removal of nitrogen from flue gases, besides the catalytic processes, which, however, give rise to technical problems because of the large spatial requirements of the catalyst masses, non-catalytic processes have also bean developed in which, in particular, the use of ammonia has found use i~
the technology because of its selective ~ction.
Disadvantages in the case of the use of ammonia include the diffiaulty of handling it and the special safety measuras necessary whlch make necessary a large technical expenditure.
Published Federal Republic of Germany Patent Specification No. 29 26 107 descrlbes a process for the removal of oxides o nitrogen, as well as possibly of halogens, sulphur and/or halogen compounds from gases, in which the gases are passed in the presence of water at temperatures below 80C. over a cyanamide or through a solution or suspension of a cyanamide and the noxious materials are separated off. However, because of the high costs of the apparatus, this 2~2~
process has not proved useful in the technology.
In the case of the process described in published Federal Republic of Germany Patent Specification No.
34 47 616, as additive for the simultaneous removal of the oxides of sulphur and nitrogen from waste gases, it is recommended to use finely-ground agents based on calcium compounds with a content of 1 to 90~ by weight of calcium cyanamide and especially of nitrogenated lime. Quite apart from the fact that the additive must be blown in in finely dispersed orm, which makes necessary a laborious grinding procedure, these dry additives based on nitrogenated lime zre comparatively inert. This has a negative effect especially in the case of those gas purification processes in which a relative high speed of reaction is necessary.
In World Intellectual Property Organisation's Patent Specification WO 87/02023, there is described a process for the reduction of emissions of oxides of nitrogen in which, besides a series of guanidine and urea compounds, calcium cyanamide is also sprayed into waste gases in the form of a solution at a temperature o~ about 1100 to 1370C. It is a disadvantage of this prscess that stable solutions of calcium cyanamide can only be produced with relative difficulty and that, in this way, only moderate rates of nitrogen removal can be achieved which are at a maximum of only about 50%.
` - 2~2~8~
Therefore, the present invention seeks to provide a process for the reduc~ion of emissions of noxious materials which does not display tha mentloned disadvantages o-f the prior art but rather makes possible an effective reduction especially of oxides of nitrogen with a low technical expense.
Thus, according to the present invention, there is provided a process for reducing the emission of noxious materials in the case of combustion processes, wherein an aqueous solution of cyanamide and/or of a hydrogen cyanamide salt is sprayed in finely-dispersed form into the combustion chamber.
Surprisingly, it has now been found that, in this way, a substantially better reduction of the values of the oxides of nitrogan can be achieved than in the case of the known processes based on the use of calcium cyanamide as additive.
In the case of the process according to the present invention, as additiYe there is used an aqueous solution of cyanamide and/or hydrogen cyanamide salts, in which case, a~ hydrogen cyanamide salts, the alkali metal and alkaline earth metal salts are to be regarded as being especially preferred because of their inexpensive availability.
As alkali metal salts, sodium and potassium hydrogen cyanamide are hereby espPcially preferred, which are obtainable from cyanamide according to known processes .
~2~
In the case of the alkaline earth metal salts, calcium and magnesium hydrogen cyanamide are especially preferably used.
According to a preferred embodiment of the process according to the presant invention, calcium dihydrogen cyanamide (Ca(HCNz )2 ) iS used which can be produced especially simply from a technical suspension of nitrogenated lime by separating the supernatant solution from insoluble residue, for example by decantation or filtration. This clsar solution, which essentially contains calcium dihydrogen cyanamide, can be used directly in the process according to the present invention without further purification.
The concéntration of the aqueous solution of cyanamide and/or hydrogen cyanamide can be varied within wide limits but, for economic reasons, it has proved to be advantageous to adjust the concentration to 5 to 50~ by weight, referred to the cyanamide content.
The aqueous solutions used according to the present invention can also contain conventional stabilizers, ~or example magnesium salts, according to published Federal Republic of Germany Patent Specification No.
32 19 054 or carboxylic acid esters according to published Federal Republic of Germany Patent Specification No. 26 42 043, which improve the storage stability of the solutions.
2~2~
It is important for the present invention that the aqueous treatment solutions are sprayed in finely dispersed form into the combustion chamber as uniformly as possible, which can be achieved without problems with the use of conventional technical means, for example nozzles. In this way, there results an optimum rate of reaction or reduction of noxious materials. The aqueous solutions can also be sprayed in with the help of carrier gases, for example the combustion air, saturated steam or other gases which behave in an inert manner and do not enter into any undesired side reactions. Preferably the aqueous solutions of cyanamide and/or hydrogen cyanamide salts are sprayed in at a pressure of from 1 to 10 bar in such a way that the droplets have a particle size of < 100 ~m.
The process according to the present invention can be used in a wide temperature range, temperatures of 300 to 1100C. and especially of 600 to 1000C.
being preferred.
The amount of additive necessary for the reduction of the emission of noxious materials depends essentially on the concentrations of noxious materials in the combustible material and can, consequently, vary in wide limits. In the case of usual combustion plants, such as garbage incineration plants and power stations, which, according to capacity, combustible material and 2~24D87 operating conditions relating to an emission of oxides of nitrogen in amounts of from 200 to 1300 mg./Nm3, normally 1 to 20 kg. of cyanamide per 1000 Nm3 of waste gas are necessary in order to achieve a degree of removal of nitrogen of > 90%. At the same time, however, there also takes place a marked reduction o other noxious materials, such as sulphur dioxide, halogens and halogenated hydrocarbons. Because of this good reduction of the amounts of noxious ma-terials, of the cost-favourable additives, as well as of the low technical expense, the process according to the present invention is outstandingly useful for use on a large scale, especially in the case of combustion processes with greatly varying emissions of noxious materials.
The ollowing Examples are given for the purposP
of illustrating the present invention:
Example 1.
In a garbage incineration plant for domestic and industrial waste, in the case of the incineration of 9 tonnes of garbage per hour, there are produced about 60,000 Nm3/hour of waste gas with an average content of oxides of nitrogen of 480 mg./Nm3 and an average oxygen content of 11%.
A 25% aqueous solution of calcium dihydrogen cyanamide (produced by mixing 637 g. of nitrogenated lime and 880 g. water, followed by separation of the supernatant solution) was sprayed with carrier 8 ~
air and atomizer air into the combus~ion chamber in an amount of 350 kg./hour ~particle size of the droplets < 25 ~m.). The content of oxides of nitrogen in the waste gas was reduced to 40 mg./Nm3, which corresponds to a degree of nitrogen removal of about 92%.
Example 2.
In the same combustion process as described in Example 1, 350 kg./hour of a 25~ aqueous cyanamide solution were sprayed into the combustion chamber with carrier air and atomizer air (particle size of the droplets ~ 25 ~m.). The content of oxides of nitrogen in the waste gas was reduced to 50 mg./Nm3, which corresponds to a degree of removal of nitrogen of about 90~.
Claims (25)
1. A process for the reduction of noxious materials in a combustion process in a combustion chamber, wherein an aqueous solution of an additive comprising at least one of cyanamide and hydrogen cyanamide salts is sprayed in finely-dispersed form into the combustion chamber.
2. A process according to claim 1, wherein said additive is alkali metal salt of hydrogen cyanamide.
3. A process according to claim 2, wherein said salt is sodium hydrogen cyanamide.
4. A process according to claim 1, wherein said additive is an alkaline earth metal salt of hydrogen cyanamide.
5. A process according to claim 4, wherein said salt is calcium dihydrogen cyanamide.
6. A process according to claim 1, 2, 3, 4, or 5, wherein said aqueous solution has a concentration of 5 to 50% by weight of said additive, referred to the cyanamide content.
7. A process according to claim 1, 2, 3, 4 or 5, wherein said aqueous solution is sprayed into the combus-tion chamber at a pressume of from 1 to 10 bar.
8. A process according to claim 6, wherein said aqueous solution is sprayed into the combustion chamber at a pressume of from 1 to 10 bar.
9. A process according to claim 1, 2, 3, 4 or 5, wherein said aqueous solution is sprayed into the combus-tion chamber with the help of a carrier gas at a pressure of from 1 to 10 bar.
10. A process according to claim 6, wherein said aqueous solution is sprayed into the combustion chamber with the help of a carrier gas at a pressure of from 1 to 10 bar.
11. A process according to claim 1, 2, 3, 4, 5, 8 or 10, wherein the droplets of the spray have a particle size adjusted to < 100 µm.
12. A process according to claim 6, wherein the droplets of the spray have a particle size adjusted to 100 µm.
13. A process according to claim 7, wherein the droplets of the spray have a particle size adjusted to 100 µm.
14. A process according to claim 9, wherein the droplets of the spray have a particle size adjusted to <
100 µm.
100 µm.
15. A process according to claim 1, 2, 3, 4, 5, 8, 10, 12, 13 or 14, wherein the spraying in is carried out at a temperature of from 300 to 1100°C.
16. A process according to claim 6, wherein the spraying in is carried out at a temperature of from 300 to 1100°C.
17. A process according to claim 7, wherein the spraying in is carried out at a temperature of from 300 to 1100°C.
18. A process according to claim 9, wherein the spraying in is carried out at a temperature of from 300 to 1100°C.
19. A process according to claim 11, wherein the spraying in is carried out at a temperature of from 300 to 1100°C.
20. A process according to claim 1, 2, 3, 4, 5, 8, 10, 12, 13, 14, 16, 17, 18 or 19, wherein said aqueous solution is sprayed in an amount of from 1 to 20 kg. of additive per 1000 Nm3 of waste gas.
21. A process according to claim 6, wherein said aqueous solution is sprayed in an amount of from 1 to 20 kg. of additive per 1000 Nm3 of waste gas.
22. A process according to claim 7, wherein said aqueous solution is sprayed in an amount of from 1 to 20 kg. of additive per 1000 Nm3 of waste gas.
23. A process according to claim 9, wherein said aqueous solution is sprayed in an amount of from 1 to 20 kg. of additive per 1000 Nm3 of waste gas.
24. A process according to claim 11, wherein-said aqueous solution is sprayed in an amount of from 1 to 20 kg. of additive per 1000 Nm3 of waste gas.
25. A process according to claim 15, wherein said aqueous solution is sprayed in an amount of from 1 to 20 kg. of additive per 1000 Nm3 of waste gas.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19893929554 DE3929554A1 (en) | 1989-09-06 | 1989-09-06 | METHOD FOR REDUCING POLLUTANT EMISSIONS IN COMBUSTION PROCESSES |
| DEP3929554.0 | 1989-09-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2024087A1 true CA2024087A1 (en) | 1991-03-07 |
Family
ID=6388711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2024087 Abandoned CA2024087A1 (en) | 1989-09-06 | 1990-08-27 | Process for the reduction of the emission of noxious materials in combustion processes |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0416562A1 (en) |
| CA (1) | CA2024087A1 (en) |
| DD (1) | DD297662A5 (en) |
| DE (1) | DE3929554A1 (en) |
| HU (1) | HU905799D0 (en) |
| NO (1) | NO903867L (en) |
| YU (1) | YU168990A (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2642043C2 (en) * | 1976-09-18 | 1986-02-06 | Buck, Alfred, 7031 Bondorf | Machine for the automatic packing of loose goods in containers such as sacks or bags |
| DE2926107C2 (en) * | 1979-06-28 | 1982-01-28 | Nukem Gmbh, 6450 Hanau | Process for separating nitrogen oxides from gases |
| DE3219054A1 (en) * | 1982-05-21 | 1983-11-24 | Skw Trostberg Ag, 8223 Trostberg | METHOD FOR INCREASING THE STORAGE STABILITY OF AQUEOUS CYANAMIDE SOLUTIONS |
| DE3447616A1 (en) * | 1983-12-30 | 1985-07-11 | Skw Trostberg Ag, 8223 Trostberg | Agents and processes for the simultaneous removal of sulphur oxides and nitrogen oxides from exhaust gases |
| DE3407689A1 (en) * | 1984-03-02 | 1985-09-12 | Steag Ag, 4300 Essen | METHOD FOR NO (ARROW DOWN) X (ARROW DOWN) REDUCTION IN FLUID BURNING FIREPLACES |
| EP0237568A4 (en) * | 1985-10-04 | 1989-01-24 | Fuel Tech Inc | Reduction of nitrogen- and carbon-based pollutants. |
| DE3815807A1 (en) * | 1988-05-09 | 1989-11-23 | Sueddeutsche Kalkstickstoff | Process for the selective noncatalytic removal of nitrogen oxides from exhaust gases |
-
1989
- 1989-09-06 DE DE19893929554 patent/DE3929554A1/en not_active Withdrawn
-
1990
- 1990-08-27 CA CA 2024087 patent/CA2024087A1/en not_active Abandoned
- 1990-09-04 EP EP90117016A patent/EP0416562A1/en not_active Withdrawn
- 1990-09-04 DD DD34381490A patent/DD297662A5/en not_active IP Right Cessation
- 1990-09-05 NO NO90903867A patent/NO903867L/en unknown
- 1990-09-05 YU YU168990A patent/YU168990A/en unknown
- 1990-09-05 HU HU579990A patent/HU905799D0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO903867L (en) | 1991-03-07 |
| DD297662A5 (en) | 1992-01-16 |
| YU168990A (en) | 1992-12-21 |
| DE3929554A1 (en) | 1991-03-07 |
| HU905799D0 (en) | 1991-03-28 |
| NO903867D0 (en) | 1990-09-05 |
| EP0416562A1 (en) | 1991-03-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |