WO1998012378A1 - Method for reducing emissions of detrimental nitrogen compounds - Google Patents
Method for reducing emissions of detrimental nitrogen compounds Download PDFInfo
- Publication number
- WO1998012378A1 WO1998012378A1 PCT/FI1997/000563 FI9700563W WO9812378A1 WO 1998012378 A1 WO1998012378 A1 WO 1998012378A1 FI 9700563 W FI9700563 W FI 9700563W WO 9812378 A1 WO9812378 A1 WO 9812378A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- boiler
- supplied
- vent gases
- furnace
- nitrogen
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910017464 nitrogen compound Inorganic materials 0.000 title claims abstract description 14
- 150000002830 nitrogen compounds Chemical class 0.000 title claims abstract description 14
- 230000001627 detrimental effect Effects 0.000 title claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 51
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000007789 gas Substances 0.000 claims abstract description 35
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 25
- 241001062472 Stokellia anisodon Species 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000000446 fuel Substances 0.000 claims abstract description 6
- 238000011084 recovery Methods 0.000 claims description 26
- 238000002485 combustion reaction Methods 0.000 claims description 14
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 210000003323 beak Anatomy 0.000 claims description 2
- 238000009993 causticizing Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000003546 flue gas Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002089 NOx Inorganic materials 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- -1 nitrogen oxides Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/06—Treatment of pulp gases; Recovery of the heat content of the gases; Treatment of gases arising from various sources in pulp and paper mills; Regeneration of gaseous SO2, e.g. arising from liquors containing sulfur compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/12—Combustion of pulp liquors
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/12—Combustion of pulp liquors
- D21C11/122—Treatment, e.g. dissolution, of the smelt
Definitions
- the invention relates to a method for reducing emissions of detrimental nitrogen compounds from the chemical cycle of a pulp mill, said method comprising supplying black liquor produced in the chemical cycle to a recovery boiler for combustion, whereby smelt is formed on the bottom of the recovery boiler as a result of the combustion, said smelt being supplied to a dissolving tank to be dissolved in a liquid containing mainly water.
- Various chemical compounds detrimental to the environment and the atmosphere are produced in a sulphate pulp mill. Examples of such compounds are various oxides of sulphur and nitrogen, and ammonia, which is formed in certain steps of the chemical cycle.
- Finnish Patent Application No. 931055 discloses a method in which oxygenous hydrocarbon obtained in the pulp cooking process, such as methanol, is supplied to the flue gases of a recovery boiler.
- oxygenous hydrocarbon obtained in the pulp cooking process such as methanol
- the methanol and any aqueous steam are supplied to the upper part of a recovery boiler to be mixed with flue gases, whereafter the flue gases are washed with white liquor or with an aqueous solution containing ammonia- and/or alkali- based compounds.
- the method is based on the fact that the nitrogen oxide NO contained in the flue gases is partly oxidated to a nitrogen dioxide N0 2 , which can be removed by an alkali scrubber.
- the drawback of this method is that it has an effect only on the reduction of the oxides of already formed nitrogen, and the only reagent that can be used is methanol or a corresponding hydrocarbon derivative.
- the method requires a flue gas scrubber suitable for removing N0 2 , and the treatment of the nitrogen compounds remaining in the washing liquid is still problematic.
- ammonia emissions are caused by nitrogen derived from wood, for example, during the combustion process of black liquor.
- the salt smelt obtained as a result of the combustion of liquor contains nitrogen compounds which are converted into ammonia during the dissolution of the smelt and in the following process steps. The ammonia produced is further released to the vent gases of the dissolving tank, for example.
- vent gases The odour of the vent gases is problematic in view of the environment, and therefore the vent gases must normally be treated. It is known to wash the vent gases of a dissolving tank with water in order to reduce ammonia emissions to the environment or to supply them with other odour gases of the pulp mill to an odour gas boiler, where they are burnt separately. This causes extra costs, and the flue gases of the odour gas boiler must still be washed in a scrubber, whereby the nitrogen compounds accumulated in the scrubber present a treatment problem.
- the object of the present invention is to provide a method for reducing emissions of detrimental nitrogen compounds from the chemical cycle of a pulp mill by which the drawbacks of the prior art solutions can be avoided.
- the method of the invention is characterized by supplying ammonia-containing vent gases separated from the smelt during the dissolution and/or in process steps following the dissolution to the furnace of a boiler of the pulp mill at a point where the fuel supplied to the boiler has mainly burnt, whereby the ammonia contained in the vent gases reacts with the nitrogen oxide present in the furnace of the boiler to form molecular nitrogen.
- the essential feature of the invention is that a detrimental nitrogen compound discharged from the chemical cycle of a pulp mill as an emission is used for removing another detrimental nitrogen compound discharged from the chemical cycle of the pulp mill so that the result is normal molecular nitrogen that can be freely discharged to the atmosphere.
- the invention has the advantage that it allows separate treatment of two detrimental compounds to be at least partly avoided, when no reagents purchased outside the mill or equipment for treating them are required for this purpose.
- the figure is a schematic view of a recovery boiler 1 , to which black liquor is supplied from an evaporator through a liquor supply channel 2.
- a smelt bed 3 is formed in the lower part of the recovery boiler.
- the smelt flows through a smelt chute 4 to a dissolving tank 5, where it is dissolved in a liquid containing mainly water, i.e. white liquor, NaOH, water or a mixture of these.
- the flue gases which are formed in the recovery boiler during the combustion and which contain nitrogen oxides flow to the upper part of the recovery boiler 1 and are discharged through a flue gas duct 6.
- such nitrogen compounds are formed in the recovery boiler 1 that once said compounds have been supplied to the dissolving tank 5 with the smelt, they are converted into ammonia.
- the ammonia is released from the solution and discharged with vent gases from the dissolving tank through a vent gas duct 7.
- the vent gases of the dissolving tank also contain aqueous steam.
- the steam is preferably removed before the vent gases are supplied to the boiler.
- a condensating scrubber 8 from which the vent gases are supplied through a duct 8a to the recovery boiler at a point where the combustion of black liquor is at least mainly completed.
- the ammonia present in the vent gases reacts with the nitrogen oxide contained in the flue gases of the recovery boiler in accordance with the following formula:
- the optimum temperature for the reaction is 900°C, but if desired the temperature window of the recovery boiler can be expanded by supplying suitable additives, such as methanol or ethanol, to the furnace. These additives can be supplied to the recovery boiler either with the ammonia- containing vent gases discharged from the dissolving tank 5 or separately from them. In view of the application of the invention, an optimal point at which the additives can be supplied to the recovery boiler 1 is below the beak 9 of the boiler, where the temperature is the most suitable for the supply of ammonia- containing vent gases. If the boiler has a so-called upper-tertiary air register, the vent gases can be supplied to the boiler 1 therethrough. Alternatively, separate feed openings can be provided for the supply of vent gases. In some cases, a tertiary air register may also be suitable for the supply of vent gases to achieve a desired effect.
- suitable additives such as methanol or ethanol
- the figure illustrates a power boiler 10 of a pulp mill, to which fuel is supplied through a fuel channel 11. Since nitrogen oxides are also formed in a conventional power boiler, the invention can also be applied by supplying ammonia-containing vent gases of a dissolving tank 5 to the power boiler 10 as shown in the figure, i.e. through channel 8a, according to the principle disclosed in connection with the recovery boiler 1.
- the ammonia-containing vent gases are supplied to a temperature of about 900°C at a point where the fuel supplied to the power boiler 10 has mainly burnt, and the nitrogen oxide is reacted with the ammonia in accordance with the formula disclosed above.
- the flue gases of the power boiler are supplied further through a flue gas duct 12.
- a significant advantage of the invention is that it allows emissions of nitrogen oxides of a boiler to be substantially reduced by utilizing another detrimental nitric compound formed in a pulp mill, i.e. ammonia.
- the nitrogen oxide and ammonia are reacted with each other to form molecular nitrogen, which is harmless and can thus be freely discharged to the atmosphere.
- the use of reagents that have to be purchased and investments in equipment can be avoided, since the necessary equipment already exists in a pulp mill.
- the invention allows considerable savings to be achieved in the treatment of flue gases and vent gases, since these gases can be treated with fewer reagents and simpler equipment.
- ammonia-containing vent gases can be supplied from the dissolving tank 5 past the scrubber 8 directly to the recovery boiler or power boiler through duct 7', indicated with broken lines, and duct 8a.
- the dissolving tank or in addition to it, it is also possible to supply ammonia- containing gases from the following process steps, such as a causticizing department.
- the temperature range of the supply point may naturally vary to a certain extent, the preferred temperature range being 800°C to 1000°C.
- the ammonia separated in a dissolving tank or in the following process steps from the smelt formed in a recovery boiler of a pulp mill is supplied to the recovery boiler or a power boiler in such a manner that, when reacting in the furnace of the boiler with the nitrogen oxide contained in the flue gases, it forms molecular nitrogen and thus reduces nitrogen oxide emissions from the boiler.
- the flue gases of both a recovery boiler and a power boiler can be further purified in a suitable manner to remove any remaining impurities.
Landscapes
- Paper (AREA)
- Treating Waste Gases (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002266492A CA2266492A1 (en) | 1996-09-20 | 1997-09-19 | Method for reducing emissions of detrimental nitrogen compounds |
BR9714340-5A BR9714340A (en) | 1996-09-20 | 1997-09-19 | Method for reducing emissions of harmful nitrogen compounds |
AU43861/97A AU4386197A (en) | 1996-09-20 | 1997-09-19 | Method for reducing emissions of detrimental nitrogen compounds |
SE9900940A SE517575C2 (en) | 1996-09-20 | 1999-03-16 | Procedure for reducing emissions of harmful nitrogen compounds |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI963758A FI963758A0 (en) | 1996-09-20 | 1996-09-20 | Foerfarande Foer att minska utslaepp av skadliga kvaevefoereningar fraon en Cellulosa Fabriks kemikaliecirkulation |
FI963758 | 1996-09-20 | ||
FI973236A FI110793B (en) | 1996-09-20 | 1997-08-05 | Procedure for reducing the emissions of harmful nitrogen compounds in the chemical circulation of a cellulose plant |
FI973236 | 1997-08-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998012378A1 true WO1998012378A1 (en) | 1998-03-26 |
Family
ID=26160217
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FI1997/000563 WO1998012378A1 (en) | 1996-09-20 | 1997-09-19 | Method for reducing emissions of detrimental nitrogen compounds |
Country Status (6)
Country | Link |
---|---|
AU (1) | AU4386197A (en) |
BR (1) | BR9714340A (en) |
CA (1) | CA2266492A1 (en) |
FI (1) | FI110793B (en) |
SE (1) | SE517575C2 (en) |
WO (1) | WO1998012378A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999047745A1 (en) * | 1998-03-19 | 1999-09-23 | Kvaerner Pulping Oy | Method for reducing emissions of detrimental nitrogen compounds of pulp mill |
EP2419197B1 (en) | 2009-04-15 | 2015-11-11 | Andritz Oy | METHOD OF REDUCING NOx-EMISSIONS USING A REACTIVE AGENT, AND CORRESPONDING BOILER |
US10206918B2 (en) | 2012-12-13 | 2019-02-19 | Immunomedics, Inc. | Efficacy of anti-HLA-DR antiboddy drug conjugate IMMU-140 (hL243-CL2A-SN-38) in HLA-DR positive cancers |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997021869A1 (en) * | 1995-12-13 | 1997-06-19 | Kvaerner Pulping Ab | PROCESS FOR OBTAINING FLUE GASES WITH LOW CONTENT OF NOx WHILE COMBUSTING BLACK LIQUOR AND A RECOVERY BOILER THEREFOR |
-
1997
- 1997-08-05 FI FI973236A patent/FI110793B/en not_active IP Right Cessation
- 1997-09-19 WO PCT/FI1997/000563 patent/WO1998012378A1/en active Application Filing
- 1997-09-19 CA CA002266492A patent/CA2266492A1/en not_active Abandoned
- 1997-09-19 BR BR9714340-5A patent/BR9714340A/en not_active IP Right Cessation
- 1997-09-19 AU AU43861/97A patent/AU4386197A/en not_active Abandoned
-
1999
- 1999-03-16 SE SE9900940A patent/SE517575C2/en not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997021869A1 (en) * | 1995-12-13 | 1997-06-19 | Kvaerner Pulping Ab | PROCESS FOR OBTAINING FLUE GASES WITH LOW CONTENT OF NOx WHILE COMBUSTING BLACK LIQUOR AND A RECOVERY BOILER THEREFOR |
Non-Patent Citations (2)
Title |
---|
DIALOG INFORMATION SERVICES, File 240, PAPERCHEM, Dialog Accession No. 00523607, Paperchem No. AB6603927, TARPEY T. et al., "Emissions of Gaseous Ammonia and Particulate Containing Ammonium Compounds from a Smelt-Dissolving Tank"; & 1995 INTERNATIONAL CHEMICAL RECOVERY CONFERENCE: PREPRINTS B (CPPA and TAPPI): B217-224, * |
TAPPI JOURNAL, Volume 76, No. 1, January 1993, MICHAEL BOBIK, "Reducing NOx Emissions from Magnesium Sulfite Liquor Boilers", pages 125-132. * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999047745A1 (en) * | 1998-03-19 | 1999-09-23 | Kvaerner Pulping Oy | Method for reducing emissions of detrimental nitrogen compounds of pulp mill |
EP2419197B1 (en) | 2009-04-15 | 2015-11-11 | Andritz Oy | METHOD OF REDUCING NOx-EMISSIONS USING A REACTIVE AGENT, AND CORRESPONDING BOILER |
US10443839B2 (en) | 2009-04-15 | 2019-10-15 | Andritz Oy | Method of reducing flue gas emissions and a boiler |
US10206918B2 (en) | 2012-12-13 | 2019-02-19 | Immunomedics, Inc. | Efficacy of anti-HLA-DR antiboddy drug conjugate IMMU-140 (hL243-CL2A-SN-38) in HLA-DR positive cancers |
Also Published As
Publication number | Publication date |
---|---|
CA2266492A1 (en) | 1998-03-26 |
AU4386197A (en) | 1998-04-14 |
BR9714340A (en) | 2000-04-11 |
FI973236A (en) | 1998-03-21 |
FI110793B (en) | 2003-03-31 |
FI973236A0 (en) | 1997-08-05 |
SE9900940D0 (en) | 1999-03-16 |
SE517575C2 (en) | 2002-06-18 |
SE9900940L (en) | 1999-03-16 |
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