+

WO2003066525A1 - Perfectionnement a la deshydratation du gypse dans la desulfuration des gaz d'emission par la modification du facies de cristaux avec des acides carboxyliques - Google Patents

Perfectionnement a la deshydratation du gypse dans la desulfuration des gaz d'emission par la modification du facies de cristaux avec des acides carboxyliques Download PDF

Info

Publication number
WO2003066525A1
WO2003066525A1 PCT/DK2003/000079 DK0300079W WO03066525A1 WO 2003066525 A1 WO2003066525 A1 WO 2003066525A1 DK 0300079 W DK0300079 W DK 0300079W WO 03066525 A1 WO03066525 A1 WO 03066525A1
Authority
WO
WIPO (PCT)
Prior art keywords
gypsum
dewatering
carboxylic acids
crystals
habit
Prior art date
Application number
PCT/DK2003/000079
Other languages
English (en)
Inventor
Anders Nimgaard Schultz
Peter Bo Olsen
Original Assignee
F.L. Smidth Airtech A/S
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by F.L. Smidth Airtech A/S filed Critical F.L. Smidth Airtech A/S
Priority to EP03706321A priority Critical patent/EP1472186A1/fr
Priority to AU2003208294A priority patent/AU2003208294A1/en
Publication of WO2003066525A1 publication Critical patent/WO2003066525A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00—Calcium sulfate cements
    • C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
    • C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than phosphogypsum
    • C04B11/264—Gypsum from the desulfurisation of flue gases
    • 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
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • 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
    • B01D53/73—After-treatment of removed components
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C01F11/464—Sulfates of Ca from gases containing sulfur oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C01F11/466—Conversion of one form of calcium sulfate to another
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00—Calcium sulfate cements
    • C04B11/02—Methods and apparatus for dehydrating gypsum
    • C04B11/028—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00—Calcium sulfate cements
    • C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • the present invention relates to dewatering of gypsum in flue gas desulfurization process based on a limestone forced oxidation technology.
  • the dewatering is enabled and/or greatly enhanced by addition of carboxylic acids, preferably citric acid to the scrubbing slurry.
  • carboxylic acids serve as a gypsum crystal habit modifier during gypsum crystallization under forced oxidation. I has been found that under normal operating conditions, i.e. when no acid is added, gypsum crystals assume acicular (needle shape) habit and are difficult to dewater since they tend to retain mother liquor in the filter cake.
  • carboxylic acids preferably citric acid
  • gypsum crystals assume columnar (bulky) habit and can be readily dewatered in the centrifuge up to 90% solids.
  • the present invention relates generally to flue gas desulfurization processes and specifically to the use of carboxylic acids to modify gypsum crystal habit in limestone forced oxidation.
  • the technique is also applicable to other technologies where gypsum is produced as for example in phosphate fertilizer or paper industry.
  • FGD flue gas desufurization
  • Gypsum scale typically forms via natural oxidation when the fraction of gypsum in slurry is greater than 15%.
  • the present invention suggests a method of enhancing dewatering and/or rendering possible dewatering of produced crystals by changing the gypsum crystal habit.
  • the present invention relates to a method for enhancing and/or enabling dewatering of gypsum produced under oxidation, preferably being forced, conditions in gas desulfurization system, such as a flue gas desulfurization system, in which system S0 2 in gas, preferably being a flue gas, is absorbed in a scrubbing liquid and neutralized with lime, such as limestone, wherein the sulfite resulting from the neutralization is oxidized to sulfate by addition of an oxidizing agent, preferably air, through one or more spargers and wherein the resulting gypsum crystal habit is modified by addition of one or more carboxylic acids, preferably citric acid, to an absorber tank where the gypsum crystal habit, in the scrubbing slurry with pH range 4-6, is changed from acicular, needle-like to bulky, columnar crystals with crystal size, preferably over 100 microns, thereby producing crystals that are easy to enrich in solids content,
  • the method for enhancing and/or enabling dewatering of gypsum produced under oxidation conditions in gas desulfurization system comprising the steps of: absorbing system S0 2 gas in a scrubbing liquid; neutralizing said scrubbing liquid with lime, wherein the sulfite resulting from the neutralization is oxidized to sulfate by addition of an oxidizing agent through one or more spargers; modifying a resulting gypsum crystal habit by adding one or more carboxylic acids to an absorber tank where the gypsum crystal habit, in the scrubbing slurry with pH range 4-6, is changed from acicular shaped crystals to bulky, columnar shaped crystals; increasing gypsum crystal concentration in scrubbing slurry using hydroclones, classifiers or thickeners; and dewatering said enriched gypsum crystals in a centrifuge, drum or belt vacuum filter.
  • the invention relates to a device for enhancing and/or enabling dewatering of gypsum produced under oxidation, preferably being forced, conditions in gas desulfurization system, such as a flue gas desulfurization system, in which device S0 2 in gas, preferably being a flue gas, is absorbed in a scrubbing liquid and neutralized with lime, such as limestone, wherein the sulfite resulting from the neutralization is oxidized to sulfate by addition of an oxidizing agent, preferably air, through one or more sparger and wherein the resulting gypsum crystal habit is modified by addition of one or more carboxylic acids, preferably citric acid, to a absorber tank, of the device, where the gypsum crystal habit, in the scrubbing slurry with pH range 4-6, is changed from acicular, needle-like to bulky, columnar crystals with crystal size, preferably over 100 microns, thereby producing gypsum crystals that are easy to
  • the device for enhancing and/or enabling dewatering of gypsum produced under oxidation conditions in gas desulfurization system comprises: means for absorbing system S0 2 gas in a scrubbing liquid; means for neutralizing said scrubbing liquid with lime, wherein the sulfite resulting from the neutralization is oxidized to sulfate by addition of an oxidizing agent through one or more spargers; means for modifying a resulting gypsum crystal habit by adding one or more carboxylic acids to a absorber tank where the gypsum crystal habit, in the scrubbing slurry with pH range 4-6, is changed from acicular shaped crystals to bulky, columnar shaped crystals; means for increasing gypsum crystal concentration in scrubbing slurry using hydroclones, classifiers or thickeners; and means for dewatering said enriched gypsum crystals in a centrifuge, drum or belt vacuum filter.
  • Preferred embodiments of the present invention comprise utilisation of or comprise a limestone forced oxidation plant.
  • the main components of limestone forced oxidation plant are preferably:
  • Gypsum dewatering comprises in general primary and secondary dewatering steps.
  • a slip stream of gypsum slurry is taken from the absorber tank and is fed to primary dewatering step at the rate to maintain material balance in the process.
  • An objective of a primary dewatering step is to increase gypsum concentration from 15% to between 30- 50% by weight.
  • Primary dewatering is typically accomplished by hydroclones, classifiers or thickeners. The underflow from hydroclone with enriched gypsum content is led to the secondary dewatering while the overflow is returned to absorber tank.
  • the secondary dewatering takes place in centrifuges, rotary or belt vacuum filters.
  • the objective of secondary dewatering is to increase solids content to up 90%.
  • the filter cake is washed with fresh water.
  • Crystallization is in the present context used preferably to denote a mass transfer operation where solute ions in solution become part of a solid crystal.
  • Supersaturation is a driving force necessary for crystal growth.
  • the solute must diffuse to the crystal surface and then become integrated into crystal lattice. Growth can therefore be diffusion-rate controlled or integration rate controlled. With low mixing intensity, growth is generally diffusion controlled while with high mixing intensity it becomes integration controlled.
  • the accepted mechanism of solute integration is the screw-dislocation theory where solute is added to the crystal at imperfections in the crystal lattice. The imperfection is continued in a spiral direction, thereby perpetuating its existence.
  • the habit of naturally grown crystals from aqueous solution varies depending on the formation conditions. This is because in the presence of foreign ions or molecules, crystal growth rates of different crystallographic surfaces can be increased or decreased.
  • gypsum produced as byproduct in flue gas desulfurization process.
  • the FGD process used at a cement manufacturing plant is based on a limestone forced oxidation.
  • gypsum has to be dewatered up to 90% solids in a centrifuge and is subsequently used in cement manufacturing. It has been found that poor dewatering can be caused by the impurities in limestone or by gypsum crystal habit.
  • gypsum crystals Under normal operating conditions, i.e. when no acid is added, gypsum crystals assume acicular (needle shape) habit and are difficult to dewater since they tend to retain mother liquor in the filter cake. The liquor is kept between crystals by capillary force.
  • gypsum crystals The size of gypsum crystals is also largely increased and this large, thick, stumpy, regular crystals can be readily dewatered in the centrifuge to 90% solids or more.
  • carboxylic acids activity is that geometric considerations relating the molecular structures of the additive and the crystal structure play an important role in determining the effect of additives on gypsum crystallization.
  • Acids having two or more carboxylic acid groups per molecule are found to be particular suited in connection with the present invention and these groups should be properly spaced in the molecule - separated by two carbon atoms in aliphatics, occupy alpha position in aromatics, and cis- position in olefins.
  • the shortest Ca ions distance at (111) face of gypsum crystals is approximately the same compared with distance between C atoms of carboxylic groups thus causing growth perpendicular to central axis.
  • carboxylic acids that are active in gypsum crystal habit change are maleic, succinic, malic, tartaric, tricarballelic, phthalic and nitrilotriacetic. These carboxylic acid will be active in all FGD processes with forced oxidation. They will be also active in other processes where gypsum is crystallized like in phosphate fertilizer and paper industry.
  • each of the one or more carboxylic acids are characterised by that at least two carboxylic groups are properly spaced in the molecule, preferably separated by two carbon atoms in aliphatics, occupy alpha position in aromatics, and cis- position in olefins.
  • Each of the one or more carboxylic acids is preferably selected from the group consisting of citric, maleic, succinic, malic, tartaric, tricarballelic, phthalic and nitrilotriacetic acids or a combination thereof. Furthermore, each of the one or more carboxylic acids when added is preferably added as a salt. Additionally, the carboxylic acids or their salts is preferably added in the amount of 20 to 2000 ppm, such as between 100-1500 ppm, preferably in the amount of 250-1000 ppm in scrubbing slurry.
  • the pH range preferably from 4-6.5, preferably at pH 5.8 in the scrubbing slurry.
  • the change of gypsum habit is preferably accomplished in a scrubbing slurry at flue gas adiabatic saturation temperature of 50-70°C, such as between 55-65°C.
  • the gypsum with changed crystal habit is preferably formed by oxidation of sulfite with oxygen in air introduced to scrubbing liquid containing carboxylic acids through sparger system.
  • the slip stream of scrubbing slurry liquor with modified gypsum crystal habit from absorber tank may be dewatered in a two stage system consisting of hydroclone(s) as a first stage and centrifuge, drum or belt vacuum filter as a second stage.
  • the filtrate separated from filter cake in dewatering equipment like centrifuge, drum or belt vacuum filter is preferably returned to an absorber tank to preserve carboxylic acids or their salts.
  • hydroclone overflow having reduced solids content characterized by gypsum crystals population of smaller size than in underflow may be returned to an absorber tank so that crystals can grow further and only hydroclone underflow having increased solids content characterized by gypsum crystals population with larger size is taken to the secondary dewatering stage.
  • the gypsum crystals with modified habit may preferably be taken from absorber tank as a scrubbing slurry slip stream and may first be enriched to 30-50% solids in the hydroclone underflow and may then be taken to the secondary dewatering stage and preferably be enriched to filter cake with over 90% solids.
  • gypsum crystals with modified habit dewatered to over 90% solids may be used in cement manufacturing or in wallboard production.
  • cement plant Such cement plants comprises preferably a device according to the second aspect of the present invention.
  • the cement plant may be adapted to carry a method according to the first aspect of the present invention.
  • Fig. 1 shows gypsum crystals without citric acid
  • Fig. 2 shows gypsum crystals with citric acid
  • Fig. 3 shows schematically a cement plant with FGC system
  • Fig. 4 shows schematically a FGD system with gypsum crystal habit modification
  • Fig. 5 is a graph showing density of absorber slurry
  • Fig. 6 is a graph showing density of Hydrocyclone underflow
  • Fig. 7 is a graph showing density of Hydrocyclone overflow
  • Fig. 8 is a graph showing residual moisture in gypsum
  • Fig 9 is a graph showing gypsum and absorber slurry purity
  • Fig. 10 is a graph showing gypsum particle size distribution of slurry produced on raw meal fines. DESCRIPTION OF PREFERRED EMBODIMENTS
  • a preferred embodiment of the present invention relates to a flue gas desulfurization plant treating gases from cement manufacturing plant.
  • the primary objective of the FGD plant is to remove sulfur dioxide by wet scrubbing of the flue gas from rotary kiln and alkali bypass. In addition, a portion of the dust and most of the halide gases are also removed.
  • the flue gas desulfurization plant consists of the following major sub-systems:
  • Figure 3 shows the schematic of cement plant where gas streams from alkali bypass, and rotary kiln are introduced to wet scrubbing system.
  • Figure 4 shows process flow diagram for flue gas desulfurization system based on limestone forced oxidation where citric acid is added for gypsum crystal modification.
  • the baghouse dust consisting of raw material fines is mixed with process water, forming an approximately 40% w/w limestone slurry.
  • the required quantity of slurry mixture is dosed into the absorber by the absorbent dosing pump based upon pH of the absorber tank liquor.
  • Flue gas from the kiln and alkali bypass is combined into a booster fan and introduced into the absorber system.
  • Pre-conditioning spray nozzles are provided at the absorber inlet to quench the gas prior to entering the absorber. Once the flue gas enters the absorber the flue gas temperature is at adiabatic saturation.
  • the absorber has three re-circulation stages which remove SO z . A portion of the dust and virtually all the halide gases are removed as well.
  • the absorber section consists of an open spray tower equipped with three spray levels, two mist eliminator sections and an integrated reaction tank complete with forced oxidation.
  • the flue gas enters the tower where it comes in contact with the three spray layers. Subsequently, the flue gas flows upwards, countercurrent to the sprayed slurry from the absorber tower re-circulation pumps.
  • the absorber tank includes side-mounted agitators which together with the recirculation pump prevent settling of gypsum in the absorber reaction tank.
  • the air for forced oxidation of sulfite to gypsum is introduced to the tank through specially designed sparger that works in conjunctions with agitators to distribute the air for intimate contact with scrubbing liquor.
  • Density control of the dewatering section ensures that the concentration of solids in the absorber slurry is maintained at a value of approx. 20% - 25% w/w.
  • Citrate solution is added to the absorber tank from citrate storage tank via dosage pump to maintain citrate concentration necessary to change gypsum crystal habit.
  • mist eliminators To remove entrained mist from the flue gas horizontal chevron type mist eliminators are provided.
  • the mist eliminators are washed intermittently by process water.
  • the slurry In order to prevent plugging during shutdowns, the slurry must be drained from the inlet and outlet pipelines of the pumps and discharged to the absorber sump. Also in the event of extended shutdowns the pump may be stopped, and consequently the systems are drained again. At shutdowns for inspection, etc. the slurry in the absorber tank is pumped to the hold-up tank. Before the absorber is started, the slurry is returned to the absorber. The gypsum crystals are needed in the process to eliminate the risk of scaling in the absorber system.
  • the evaporation of water in the absorber is compensated by adding quench water, water in the slurry, water added through the oxidation system, and water in the mist eliminator wash.
  • Waste water is purged out of the system from the collecting tank.
  • the purpose of the purge is to avoid accumulation of impurities in the system.
  • the slurry solid concentration in the absorber tank is suitable for dewatering the gypsum to 90% or more solids content by means of a two stage dewatering system consisting of primary and secondary steps.
  • the slip stream of scrubbing slurry is taken to dewatering at the rate to maintain material balance in the FGD process.
  • hydroclone An important role of hydroclone is to segregate solids by their particle size.
  • the underflow with enriched solids content has gypsum crystal population with larger size.
  • the overflow with reduced solids content has gypsum crystal population with smaller size and it contains some unreacted limestone.
  • the overflow of the hydrocyclone battery is returned to the absorber so that gypsum crystals can grow further and unreacted limestone can be reused.
  • the filtrate from the centrifuge is also returned to absorber tank to preserve citrate solution.
  • the dewatered gypsum is stored and is used in cement manufacturing.
  • a full scale FGD system has been installed at a cement plant where by-product gypsum is used in cement production.
  • the schematics of the installation are shown in figures 3 and 4 while the process description and list of equipment is presented above.
  • the key process parameters are:
  • the limestone with varying quality from a local quarry is used as absorbent for ⁇ 0 2 removal.
  • Figure 5 shows the absorber density during the two test periods. As can be seen the density in the absorber has been controlled very close to the preferred operating range of 1,110-1,120 kg/m 3 .
  • the density in the underflow of the hydro cyclones (HC) is the best indicator for the crystal habit. If the underflow density starts to decrease without obvious reason like change in feed density, temperature, etc., it is an indication that the crystal size or habit of the gypsum crystals are changing. In the test conducted, the HC underflow was followed very closely. Figure 6 shows the changes in HC underflow as a function of time for one test period.
  • the steady state density of the hydro cyclone underflow will be 1350-1400 kg/m 3 with the raw meal fines combined with the addition of citric acid as absorbent.
  • the density in the overflow varies between 1,015 and 1,090 kg/m 3 during the operation.
  • the residual moisture in the produced gypsum for the combined operation on raw meal fines and citric acid is slightly higher than the guaranteed 10 wt-%. It is also noted that the trend of the residual moisture follows the trend in the hydro cyclone overflow density.
  • Figure 10 shows the particle size distribution of slurry produced in the absorber.
  • the desired PSD is indicated by the "As specified to the supplier of dewatering equipment" curve. The difference between the three PSD's are very small, indicating that stable operation has been achieved.
  • the enhancement of gypsum dewatering through gypsum crystal habit modification is also applicable to industries where gypsum is produced and has to be dewatered.
  • the major such industries are phosphate fertilizer plants, paper industry, oil refineries, waste water treatment, etc.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)

Abstract

La présente invention a trait à la déshydratation du gypse dans le procédé de désulfuration des gaz d'émission basé sur la technologie d'oxydation forcée de calcaire. La déshydratation est activée et/ou améliorée par l'ajout d'acides carboxyliques, de préférence l'acide citrique à la suspension de lavage. On a observé que les acides carboxyliques agissent comme agent modificateur du faciès des cristaux lors de la cristallisation du gypse sous oxydation forcée. On a également observé que dans des conditions de fonctionnement normales, c'est à dire en l'absence d'ajout d'acide, le faciès de cristaux du gypse présente un faciès aciculaire (en forme d'aiguille) et leur déshydratation est rendue difficile par le fait qu'ils ont tendance à retenir la solution-mère dans le gâteau de filtration. En présence d'acides carboxyliques, de préférence d'acide citrique, dans la suspension de lavage les cristaux présentent un faciès allongé (massif) et peuvent être aisément déshydratés dans la centrifugeuse jusqu'à 90 % en matières solides. L'invention a trait également à un dispositif permettant la déshydratation du gypse et une cimenterie comportant un tel dispositif.
PCT/DK2003/000079 2002-02-08 2003-02-07 Perfectionnement a la deshydratation du gypse dans la desulfuration des gaz d'emission par la modification du facies de cristaux avec des acides carboxyliques WO2003066525A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP03706321A EP1472186A1 (fr) 2002-02-08 2003-02-07 Perfectionnement a la deshydratation du gypse dans la desulfuration des gaz d'emission par la modification du facies de cristaux avec des acides carboxyliques
AU2003208294A AU2003208294A1 (en) 2002-02-08 2003-02-07 Improvement of flue gas desulfurization gypsum-dewatering through crystal habit modification by carboxylic acids

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US35448802P 2002-02-08 2002-02-08
DKPA200200192 2002-02-08
DKPA200200192 2002-02-08
US60/354,488 2002-02-08

Publications (1)

Publication Number Publication Date
WO2003066525A1 true WO2003066525A1 (fr) 2003-08-14

Family

ID=27735955

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DK2003/000079 WO2003066525A1 (fr) 2002-02-08 2003-02-07 Perfectionnement a la deshydratation du gypse dans la desulfuration des gaz d'emission par la modification du facies de cristaux avec des acides carboxyliques

Country Status (3)

Country Link
EP (1) EP1472186A1 (fr)
AU (1) AU2003208294A1 (fr)
WO (1) WO2003066525A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108619884A (zh) * 2017-03-24 2018-10-09 中国石油化工股份有限公司 烟气脱硫塔和烟气除尘、脱硫及废水处理方法
CN112174185A (zh) * 2020-10-18 2021-01-05 山东泰尊智能装备有限公司 一种柠檬酸石膏全自动生产工艺
CN112540158A (zh) * 2020-11-25 2021-03-23 广西电网有限责任公司电力科学研究院 石灰石湿法脱硫强制氧化空气利用率的测试方法
CN113634113A (zh) * 2021-07-08 2021-11-12 中国大唐集团科学技术研究院有限公司华东电力试验研究院 一种用于解决脱硫石膏浆液脱水困难的方法
CN114890697A (zh) * 2022-05-20 2022-08-12 中南大学 石膏复合转晶剂及其在制备α-半水石膏中的应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112520823B (zh) * 2020-11-10 2022-10-11 河北国华定州发电有限责任公司 改善脱硫浆液结晶品质的复合石膏结晶促进剂的添加方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2372651A1 (fr) * 1976-12-03 1978-06-30 Hoelter H Procede pour la purification des gaz bruts et d'autres gaz residuaires qui contiennent de l'anhydride sulfureux et dispositif pour l'execution de ce procede
JPH0489400A (ja) * 1990-07-31 1992-03-23 Nkk Corp 針状石膏結晶の製造方法
US5211928A (en) * 1991-10-15 1993-05-18 Calgon Corporation Method of improving gypsum slurry filtration in the production of phosphoric acid
US5246677A (en) * 1991-05-07 1993-09-21 Electric Power Research Institute Addition of organophosphonates for size control of wet calcium-based FGD byproduct solids under forced oxidation conditions
US5486342A (en) * 1994-06-13 1996-01-23 Electric Power Research Institute Clear liquor scrubbing of sulfur dioxide with forced oxidation in flue gas desulfurization system
US5500197A (en) * 1990-10-30 1996-03-19 Metallgesellschaft Aktiengesellschaft Process of purifying gypsum
EP0706814A1 (fr) * 1994-10-12 1996-04-17 Mitsubishi Jukogyo Kabushiki Kaisha Dispositif pour la désulfuration par voie humide de gaz de fumée

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2372651A1 (fr) * 1976-12-03 1978-06-30 Hoelter H Procede pour la purification des gaz bruts et d'autres gaz residuaires qui contiennent de l'anhydride sulfureux et dispositif pour l'execution de ce procede
JPH0489400A (ja) * 1990-07-31 1992-03-23 Nkk Corp 針状石膏結晶の製造方法
US5500197A (en) * 1990-10-30 1996-03-19 Metallgesellschaft Aktiengesellschaft Process of purifying gypsum
US5246677A (en) * 1991-05-07 1993-09-21 Electric Power Research Institute Addition of organophosphonates for size control of wet calcium-based FGD byproduct solids under forced oxidation conditions
US5211928A (en) * 1991-10-15 1993-05-18 Calgon Corporation Method of improving gypsum slurry filtration in the production of phosphoric acid
US5486342A (en) * 1994-06-13 1996-01-23 Electric Power Research Institute Clear liquor scrubbing of sulfur dioxide with forced oxidation in flue gas desulfurization system
EP0706814A1 (fr) * 1994-10-12 1996-04-17 Mitsubishi Jukogyo Kabushiki Kaisha Dispositif pour la désulfuration par voie humide de gaz de fumée

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199219, Derwent World Patents Index; Class L02, AN 1992-154467, XP002214404 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108619884A (zh) * 2017-03-24 2018-10-09 中国石油化工股份有限公司 烟气脱硫塔和烟气除尘、脱硫及废水处理方法
CN108619884B (zh) * 2017-03-24 2020-11-06 中国石油化工股份有限公司 烟气脱硫塔和烟气除尘、脱硫及废水处理方法
CN112174185A (zh) * 2020-10-18 2021-01-05 山东泰尊智能装备有限公司 一种柠檬酸石膏全自动生产工艺
CN112540158A (zh) * 2020-11-25 2021-03-23 广西电网有限责任公司电力科学研究院 石灰石湿法脱硫强制氧化空气利用率的测试方法
CN113634113A (zh) * 2021-07-08 2021-11-12 中国大唐集团科学技术研究院有限公司华东电力试验研究院 一种用于解决脱硫石膏浆液脱水困难的方法
CN114890697A (zh) * 2022-05-20 2022-08-12 中南大学 石膏复合转晶剂及其在制备α-半水石膏中的应用

Also Published As

Publication number Publication date
EP1472186A1 (fr) 2004-11-03
AU2003208294A1 (en) 2003-09-02

Similar Documents

Publication Publication Date Title
US5362458A (en) Process for the simultaneous absorption of sulfur oxides and production of ammonium sulfate
JP3881375B2 (ja) 煙道ガス洗浄装置
US8337790B2 (en) System and method for purification of flue gases
US20100074828A1 (en) Method and Apparatus for the Removal of Carbon Dioxide from a Gas Stream
US4246245A (en) SO2 Removal
RU2040960C1 (ru) Способ удаления оксидов серы из топочных газов и установка для его осуществления
CN86106161A (zh) 同时进行氧化硫吸收和生产硫酸铵的方法和设备
US8425868B2 (en) Method for preventing re-emission of mercury from a flue gas desulfurization system
JPH0255095B2 (fr)
US20030175193A1 (en) FGD gypsum dewatering improvement through crystal habit modification by carboxylic acids
US7419643B1 (en) Methods and apparatus for recovering gypsum and magnesium hydroxide products
CN106178896A (zh) 一种氨水循环利用的脱硫装置及方法
US5645807A (en) Magnesium-enhanced sulfur dioxide scrubbing with gypsum formation
CA2239390A1 (fr) Processus de desulfuration des effluents gazeux
JP3751340B2 (ja) 排ガスの脱硫方法
US4388283A (en) SO2 removal
KR950010795B1 (ko) 탈황 방법과 장치
US3980756A (en) Air pollution control system
CN101085411A (zh) 一种烟气净化装置和方法
FI84435C (fi) Foerfarande och anordning foer rengoering av foeroreningar innehaollande gaser
US5733517A (en) Byproduct solids crystal modification with organic acids in wet flue gas desulfurization systems
US5082639A (en) Sulfur dioxide removal from gases using a modified lime
US4080427A (en) Method of desulfurizing exhaust gases by wet lime-gypsum process
WO2003066525A1 (fr) Perfectionnement a la deshydratation du gypse dans la desulfuration des gaz d'emission par la modification du facies de cristaux avec des acides carboxyliques
US3989464A (en) Sulfur dioxide scrubbing system

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2003706321

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2003706321

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP

WWW Wipo information: withdrawn in national office

Ref document number: 2003706321

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载