EP1271053A2 - Procédé pour incinérer des déchets à forte teneur en halogènes en réduisant les émissions nocives ainsi que la corrosion - Google Patents

Procédé pour incinérer des déchets à forte teneur en halogènes en réduisant les émissions nocives ainsi que la corrosion Download PDF

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Publication number
EP1271053A2
EP1271053A2 EP02013485A EP02013485A EP1271053A2 EP 1271053 A2 EP1271053 A2 EP 1271053A2 EP 02013485 A EP02013485 A EP 02013485A EP 02013485 A EP02013485 A EP 02013485A EP 1271053 A2 EP1271053 A2 EP 1271053A2
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EP
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Prior art keywords
sulfur
halogen
waste
flue gas
boiler
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Granted
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EP02013485A
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German (de)
English (en)
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EP1271053A3 (fr
EP1271053B1 (fr
Inventor
Bernhard Prof. Dr. Vosteen
Joachim Beyer
Peter Krippner
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Currenta GmbH and Co OHG
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Bayer AG
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
    • F23J15/04—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material using washing fluids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/08—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating
    • F23G5/14—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating including secondary combustion
    • F23G5/16—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating including secondary combustion in a separate combustion chamber
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/50—Control or safety arrangements
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2207/00—Control
    • F23G2207/60—Additives supply

Definitions

  • the invention relates to the low-corrosive and low-emission co-incineration of highly halogenated waste, preferably liquid waste, in a waste incineration plant.
  • Undesirable free halogens such as free chlorine Cl 2 , free bromine Br 2 and / or free iodine I 2 form partly already in the furnace and then - to a greater extent - with the beginning of flue gas cooling in the subsequent boiler.
  • the temperature-dependent, kinetically limited replication of free halogens from the corresponding hydrogen halides follows the so-called Deacon reaction, which, inevitably, is strongly inhibited. Due to the regulated addition of sulfur to the combustion chamber of the waste incineration plant and the SO 2 formed as a result of combustion, it is possible to largely suppress these free halogens in the boiler, ie on the way to the end of the flue gas.
  • a waste incinerator is described, for example, in H.W. Fabian et al. [1].
  • Typical waste incinerators include a primary furnace (e.g. Rotary kiln), a secondary combustion chamber (secondary combustion chamber), a waste heat boiler, sometimes also an electrostatic or filtering dust collector, a Flue gas scrubbing with e.g. one - stage or multi - stage acid laundry (quenches and e.g. acid rotary atomizer scrubber) and alkaline wash (e.g., alkaline Rotary atomizer scrubber), optionally also with a mist eliminator and e.g. a condensation electrostatic precipitator.
  • a primary furnace e.g. Rotary kiln
  • secondary combustion chamber secondary combustion chamber
  • a waste heat boiler sometimes also an electrostatic or filtering dust collector
  • Flue gas scrubbing with e.g. one - stage or multi - stage acid laundry (quenches and e.g. acid rotary atomizer scrub
  • the ratio of sulfur and chlorine in the burned waste menu should be such as to give a "molar ratio of sulfur / chlorine>1".
  • chlorine meaning free chlorine
  • the object of the invention is therefore to provide a method for corrosion and Low-emission co-incineration of highly halogenated waste in waste incineration plants with minimal use of resources and minimal waste accumulation to find.
  • the solution of the object according to the invention consists in a method and a Apparatus for low-corrosion and low-emission co-combustion of highly halogenated Liquid wastes in waste incineration plants with at least one combustion chamber, a waste heat boiler, a flue gas scrubber (e.g., consisting of a on or multi-stage acid laundry and alkaline laundry), whereby the firebox, in addition to other sulphurous waste, solid or liquid sulfur or corresponding sulfur carriers, e.g. Waste sulfuric acid are added metered.
  • the regulation of the addition of sulfur or corresponding sulfur carriers takes place - essentially - proportionally to the current total halogen load (e.g. the chlorine and / or bromine total freight) in the flue gas.
  • the sulfur may be in the form of solid sulfur in the primary or secondary combustion chamber, Liquid sulfur or other sulfur carriers, e.g. Waste sulfuric acid, be added directly.
  • Solid sulfur is preferably added in pelleted or granulated form.
  • This form of addition has the advantage that the pelleted or granulated solid sulfur (For example, so-called sulfur granules) can be handled safely and well dosed, better than e.g. powdery sulfur flower.
  • the sulfur granules are preferred added pneumatic entry into the primary furnace.
  • the entry of the Sulfur granules should with a controllable dosing and delivery unit such as Metering screw or vibrating trough done.
  • Preferred is a variable speed Dosing screw with subsequent injector and pneumatic delivery line to the combustion chamber, preferably to the head of the rotary kiln ("blowing the sulfur granules").
  • Waste sulfuric acid is transferred by means of a controllable dosing pump Atomizing nozzles or corresponding nozzles in the primary or secondary Firebox added.
  • the addition of sulfur or other sulfur carriers in the furnace is according to the invention - starting from the current flue gas halogen total freight - to regulate so that a calculated target SO 2 content in the flue gas before boiler or - alternatively - a corresponding target SO 2 - Residual content in the boiler raw gas before quenching is continuously maintained.
  • the controlled addition of sulfur or sulfur carriers should sufficiently but not excessively increase the SO 2 supply in the boiler flue gas.
  • the required for the suppression of free halogens in the boiler as well as for hypochlorite reduction in the subsequent alkaline scrubbing SO 2 demand increases with the halogen total freight, ie the necessary SO 2 content in the flue gas before boiler (after afterburning) or the corresponding SO 2 residual content in the boiler raw gas after boiler (before quenching) must be raised with the total halogen load.
  • the proportion of free halogens in the total halogen load in the case of bromine or even iodine is considerably greater than in the case of chlorine and thus also the specific, ie related to the total flue gas total halogen demand for sulfur.
  • the halide load of acid wastewater is thus a good measure of total halogen freight the boiler flue gas, at least in steady-state operation, because with constant admission, the total halogen load of the boiler flue gas both in the case of chlorine and in the case of bromine - with sufficient supply of sulfur - to about 99% with the halide load of the waste water of the acid wash identical.
  • the halide concentration in the acid wastewater is e.g. from a conductivity measurement.
  • the electrical conductivity of aqueous halide solutions strongly temperature-dependent; therefore, in the conductivity measurement for Temperature compensation integrated a temperature measurement.
  • the associated halide freight in acidic wastewater results then by the multiplication of the halide concentration with the e.g. Measured by inductive flow meter Volume flow of acid wastewater.
  • the current total flue gas halogen freight could also directly, but comparatively expensive from the HX and X 2 contents in the boiler raw gas and from the flue gas volume flow or a size proportional to the flue gas volume flow Steam output of the boiler can be determined; For this purpose, for example, with measuring instruments based on near-infrared spectrometry, the HX and X 2 contents in the boiler raw gas would have to be measured before quenching.
  • the bisulfide formed in-process from the residual SO 2 of the boiler raw gas in the alkaline scrubber is known not to be stable to oxidation, ie it not only serves the desired reduction of hypochlorite (NaOCl) but also reacts with dissolved oxygen at the same time.
  • the residual SO 2 content required in the case of chlorine in the crude boiler gas before quenching is therefore considerably higher than the Cl 2 residual charge chemisorbed in the alkaline scrubbing - stoichiometrically seen - would correspond.
  • the sulfur dosing ramp can be determined operationally, for example in the case of chlorine, by carrying out a required "operating test at a preselected high total chlorine load" and starting it with an initially greatly increased supply of sulfur and, consequently, a greatly increased SO 2 residual content in the boiler raw gas before quenches (after kettle). Consequently, in the alkaline scrubber initially there is also a considerable supply of bisulfide; On the other hand, there is no hypochlorite and correspondingly in the clean gas after alkaline scrubbing initially no free chlorine is detectable. Then the amount of sulfur is lowered gradually until free chlorine is detectable on the clean gas side.
  • the preselected total chlorine load or the corresponding preselected Cl ges concentration in the boiler raw gas (mg Cl ges / Nm 3 tr. ).
  • the SO 2 residual content thus determined in the boiler raw gas in which free chlorine is noticeably detectable, form a point of the sulfur metering ramp.
  • this one point is sufficient to set a sulfur metering ramp as the relationship between the total chlorine load or the Cl ges concentration in the flue gas on the one hand and the necessary minimum value of the continuously measured residual SO 2 content in the boiler raw gas before quenching (after boiler) on the other hand because the sulfur metering ramp is the straight line through this one measuring point and the origin of the coordinates.
  • the straight line thus determined indicates with sufficient accuracy for a wide range of chlorine contents which target SO 2 residual content in the boiler raw gas must be maintained before quenching (according to the boiler) at different total chlorine loadings so that sufficient bisulfide is always present in the alkaline wash and the hypochlorite desired there Reduction takes place, so that hardly any free chlorine Cl 2 is found in the clean gas after the alkaline wash or only a minimal, below a predetermined limit lying Cl 2 -Reingaskonzentration.
  • a corresponding plant-specific sulfur dosing ramp for dosing Sulfur can also be detected in the case of bromine or iodine.
  • the SO 2 content in the flue gas upstream of the boiler (not operationally measured) must be significantly higher than the SO 2 residual content in the boiler raw gas before quenching (according to the boiler).
  • the determination of the difference, ie the halogen-related SO 2 consumption in the boiler can be calculated: For example, the actual chlorine total load (or the corresponding chloride load in acid wastewater) with the plant-specific Cl 2 conversion in the boiler (eg 3 % of the total chlorine load, namely 75% of a total of 4%), this value then divided by the molecular weight of Cl 2 (70.914 kg Cl2 / kmol) and finally with the molecular weight of sulfur dioxide (64.06 kg S / kmol) to multiply.
  • the flue gas-side bromine total freight or the wastewater-side bromide freight is multiplied by the plant-specific proportion of intermediate free bromine determined for the case of bromine. According to our field trials, this proportion ranges from 40% at low total bromine loads to 65% at high total bromine loads, so it is much larger than in the case of chlorine. In contrast to the free chlorine, the free bromine still largely reacts with SO 2 in the boiler (presumably to SO 2 Br 2 ), namely> 90%. Approximately in the boiler, a 100% Br 2 conversion is assumed.
  • the total intermediate Br 2 load is divided by the molecular weight of Br 2 (159.88 kg Br 2 / kmol) and multiplied by the molecular weight of sulfur dioxide (64.06 kg S / kmol).
  • the sulfur consumption due to the oxidative SO 2 / SO 3 conversion is also taken into account here, as described above.
  • free chlorine or bromine which penetrates into the clean gas is measured by direct measurement of the Cl 2 or Br 2 content in the clean gas after alkaline scrubbing (eg after induced draft, but mind before an optionally downstream SCR catalyst bed), preferably by means of an electrochemical measuring cell, such as the so-called chemosensor from Drägerbuttechnik (see [8]).
  • the sample gas is continuously withdrawn from the flue gas channel in the bypass, dried and then analyzed in the chemosensor.
  • Free chlorine (or free bromine) causes a voltage change in the measuring cell of the chemosensor, which is converted into a concentration.
  • the primary Cl 2 readings should be continuously corrected for the NO x -based Cl 2 indication using the current NO x gas content.
  • Cl 2 or Br 2 levels in the clean gas after flue gas scrubbing eg, after induced draft, but mind before any downstream SCR catalyst bed
  • another continuously indicating Cl Position 2 - or / and Br 2 - measuring device eg a device based on near-infrared spectrometry.
  • the target SO 2 content (be it the computationally controlled target SO 2 content in the flue gas before boiler or via a conductivity and wastewater flow measurement directly controlled target SO 2 residual content in the boiler raw gas before quenching ) despite the control intervention by the primary control loop is not sufficiently fast adapted to the current halogen total freight, so that it can lead in the meantime to a SO 2 deficiency and consequently to an undesirable breakdown of eg free Cl 2 or Br 2 into the clean gas after alkaline scrubbing.
  • the metered amount of sulfur must be raised in time and in the meantime increased as long, for example by 5-100%, preferably by 10-50%, to the requested by the primary loop sulfur again alone for the X 2 Suppression and the NaOX reduction is sufficient.
  • the target residual SO 2 content in the boiler raw gas before quenching is reduced by up to 1000 mg SO 2 / Nm 3 tr via an "extended control loop". increases, for example, in the case of chlorine from a Cl 2 content in the clean gas ⁇ 0.5 mg Cl 2 / Nm 3 tr and increasingly with the level of Cl 2 content measured in the clean gas. This ensures that there is always a sufficiently large excess of SO 2 even in the event of an abrupt increase in the chlorine reactor in the crude boiler gas before quenching.
  • the amount of sulfur can also at the corresponding first increase of the Halide load in acid wastewater (as an indication of an erratic Increase in total halogen load), preferably proportional to observed rate of increase of conductivity.
  • the inventive method for the controlled suppression of free halogens may also apply mutatis mutandis to discontinuous waste disposal ("container operation") be used.
  • the dosage of sulfur and / or to couple other sulfur carrier with the package task i. to raise periodically and - depending on the halogen or halide content of the container - both in terms Height, time and duration of the associated sulfur dosage shot.
  • the amount of time, the amount of time and the time attached to the task the container size coordinated dosage of sulfur and / or other sulfur carriers can automatically read in individual bar codes to calorific value, Halogen type and halogen quantity of the individual containers fall back.
  • the device is for metered addition
  • a metering screw with subsequent pneumatic preferred Conveyor line to the primary furnace is for metered addition
  • a metering screw with subsequent pneumatic preferred Conveyor line to the primary furnace is
  • the metering device is used of the sulfur preferably a metering pump with subsequent nozzle or Nozzle, over which atomizing in the primary or secondary firebox is injected.
  • the inventive method has the advantage that free halogens such as Cl 2 and / or Br 2 are eliminated by the controlled addition of sulfur or other sulfur carriers in the furnace equal to two points of the incinerator, namely once in the waste heat boiler (direct gas phase reaction with SO 2 ) and in alkaline washing (hypohalide reduction with chemisorbed residual SO 2 formed bisulfide).
  • FIG. 1 shows a typical waste incineration plant (here the hazardous waste incineration plant).
  • FIG. 2 shows, by way of example for the case of chlorine, ie the combustion of highly-chlorinated waste, a "closed sulfur balance via firing, boiler and acid wash".
  • This representation provides evidence that in the boiler about 3% of the total chlorine load as an intermediate Cl 2 still react in the boiler by means of SO 2 back to HCl and SO 3 ;
  • the SO 3 formed is found in the acidic quenching wastewater as SO 4 2- again.
  • the operational tests for FIG. 2 were carried out under a constant high sulfur supply with progressively increasing overall chlorine load.
  • the abscissa of the diagram is the total chlorine content, based on the dry flue gas volume flow, thus described as mg Cl ges / Nm 3 tr .
  • Figure 3 shows the associated chlorine balance, now including the alkaline wash (alkaline rotary atomizer scrubber (ARW)) to exemplify that - with sufficient supply of sulfur - 99% of total chlorine load as HCl in the acidic laundry and only 1% of total chlorine load as Cl 2 get into the alkaline wash and there (over the residual SO 2 in the boiler raw gas before quenching) are ultimately reduced to the stable chloride.
  • alkaline wash alkaline rotary atomizer scrubber (ARW)
  • FIG. 4 shows, by way of example for the case of chlorine, the primary control circuit with use of the chlorine-specific sulfur metering ramp 13, guided by the residual SO 2 -SOLL value 14 a in the boiler raw gas 14, before quenching on the basis of the halide load in the quenching waste water;
  • the latter is determined from the HCl content 15 in the wastewater (determined by means of temperature-compensated conductivity measurement 16) by multiplication with the wastewater volume flow 17 (MID measurement).
  • the manipulated variable is the speed of the metering screw drive 21. This speed is changed via the PI controller R.3332 22.
  • This regulator 22 continuously compensates for the residual SO 2 -IST value 14a measured behind the waste heat boiler 5 with the residual SO 2 -SOLL value 23 required according to the sulfur metering ramp 13.
  • FIG. 5 shows, again by way of example in the case of chlorine, the operationally predetermined chlorine-specific metering ramp used in the primary control circuit (FIG. 4). For their determination, 6 combustion tests with different total loads were carried out. The main parameters of these operating tests are given in Table 1. In each of the operating experiments, the throughput of a highly chlorinated liquid waste mixture of dichloropropane DCP and chlorinated hydrocarbon CKW (each with known chlorine contents) was kept constant.
  • the respective chlorine load (based on the dry flue gas volume flow of about 40000 Nm 3 tr. / H) can be read as the abscissa in Figure 5; the ordinate in FIG. 5 indicates the necessary residual SO 2 desired value (minimum SO 2 residual content) in the boiler raw gas before quenching, based on the dry flue gas volume flow.
  • FIG. 6 for experiment 4 in table 1 exemplifies the procedure for determining a point of the sulfur metering ramp.
  • the diagram shows the contents of residual SO2 in the boiler raw gas (left ordinate) and of free chlorine in the clean gas after alkaline scrubbing, measured downstream of the induced draft (right ordinate) as a function of the test time.
  • a high residual SO 2 content in the boiler raw gas was preselected and then slowly lowered at the start of the experiment.
  • the Cl 2 concentration in the clean gas before SCR starts to increase slightly until after about 12:30 h at about 500 mg residual SO 2 / Nm 3 tr.
  • FIG. 8 shows the shortage of SO 2 due to a sudden increase in freight due to this delay as a result of trailing detection of the current total halogen load as well as the still-observable Cl 2 breakthrough into the clean gas after alkaline scrubbing when the primary control circuit is operated alone.
  • the primary control circuit After the primary control loop has been put into operation at 1:45 pm, the primary control circuit initially restores the SO 2 residual content in the boiler raw gas from the preselected value to the value actually required according to the sulfur metering ramp.
  • the deliberately induced jump in the chlorine reactor from 900 kg / h to 1400 kg / h took place here (see Figure 7).
  • a Chemosensor 25 from the company Drägerbuttechnik is preferably used for this measurement of the free chlorine.
  • the sample gas is continuously withdrawn from the flue gas channel, dried and analyzed.
  • the free chlorine causes in the measuring cell of the chemosensor 25 a voltage change, which is converted into a concentration.
  • the primary Cl 2 measured values from the sensor 25 are corrected with respect to the NO x -induced dummy display with device-specific correction factors 27 (calculation of the dummy display 28, subtraction of FIG Apparent indication of primary Cl 2 reading 29).
  • the NO x -corrected Cl 2 reading is from a preselectable Cl 2 content 30 in the clean gas of, for example, 0.5 mg Cl 2 / Nm 3 tr.
  • the regulator R.3401 31 in an additional SO 2 request implemented, which can be raised in the amplifier 32 again by a preselectable gain factor 33, for example the factor 10.
  • This additional SO 2 request is added to the SO 2 request from the primary control loop in the "disturbance adder" 34.
  • the SO 2 -SOLL value 23 increases by z. B. 1000 mg SO 2 / Nm 3 tr.
  • the controller 22 is now again equal to the residual SO 2 -IST value 14a measured downstream of the waste heat boiler 5 with the residual SO 2 -SOLL value 23 increased in accordance with the interference variable connection described above from
  • the temporal increase in chloride load in the quench wastewater can also be utilized, eg via a DIF (differentiation of the time increase 24) in order to increase the residual SO 2 in the event of a rapid increase.
  • Target value 23 to be increased immediately.
  • All measures for temporary raising of the residual SO 2 -SOLL value 23 via the solely on the sulfur addition ramp 13 lagging requested residual SO 2 -SOLL value addition may together (addition in disturbance adding unit 34), or be used separately.
  • the regulator R. 3401 causes a leading increase in the residual SO 2 -SOLL value and thus a rapid increase in the CO 2 actual SO 2 residual content in the boiler raw gas before quenching by about 1000 mg SO 2 / Nm 3 tr. Accordingly, there is no Cl 2 breakthrough, but rather the Cl 2 content in the clean gas immediately returns to values ⁇ 0.5 mg / Nm 3 tr. Back.
  • FIG. 13 shows, in the case of bromine, that in the boiler a Br 2 content of on average about 61% of total bromine (instead of 3% in the case of chlorine) is converted. Note: The brominated liquid waste burned in the experiment contained about 25% bromine and about 3% chlorine; this chlorine is taken into account in FIG. 13, ie the evaluation result shown is "chlorine-purified".
  • FIG. 14 shows, in the case of bromine, that also here only about 1% of the total load gets into the alkaline wash, i. Despite the a significantly higher proportion of free bromine in the total bromine total freight sufficient sulfur supply - here too 99% of total bromine in the acidic laundry deposited.
  • FIG. 15 shows the comparison of the conductivity (temperature-compensated to FIG 20 ° C) of aqueous HCl and HBr solutions.
  • FIG. 16 shows the above-mentioned fact that the free chlorine in the clean gas passage through a downstream clean gas SCR according to the Chloro-Deacon Reaction Catalyzed on the Metal-Oxide-Rich SCR Catalyst - Under the pure gas conditions available there (low residual chlorine, high Water vapor content, about 300 ° C) - largely reacted back to HCl.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Treating Waste Gases (AREA)
  • Incineration Of Waste (AREA)
  • Gasification And Melting Of Waste (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Processing Of Solid Wastes (AREA)
EP02013485A 2001-06-29 2002-06-17 Procédé d'incinération de déchets à forte teneur en halogènes afin de réduire les émissions nocives et la corrosion Expired - Lifetime EP1271053B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10131464A DE10131464B4 (de) 2001-06-29 2001-06-29 Verfahren zur korrosions- und emissionsarmen Mitverbrennung hochhalogenierter Abfälle in Abfallverbrennungsanlagen
DE10131464 2001-06-29

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EP1271053A2 true EP1271053A2 (fr) 2003-01-02
EP1271053A3 EP1271053A3 (fr) 2003-05-02
EP1271053B1 EP1271053B1 (fr) 2007-11-14

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US (1) US20030065236A1 (fr)
EP (1) EP1271053B1 (fr)
JP (1) JP4221194B2 (fr)
AT (1) ATE378554T1 (fr)
DE (2) DE10131464B4 (fr)
DK (1) DK1271053T3 (fr)
ES (1) ES2295258T3 (fr)
HU (1) HU228684B1 (fr)
PL (1) PL199924B1 (fr)

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US7615101B2 (en) * 2005-09-07 2009-11-10 Energy & Environmental Research Foundation High energy dissociation for mercury control systems
DE102006016963B3 (de) * 2006-04-11 2007-10-04 Forschungszentrum Karlsruhe Gmbh Verfahren und Vorrichtung zur Reduzierung von Stickoxiden und halogenierten organischen Verbindungen in Verbrennungsanlagen
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CN105502543A (zh) * 2016-01-15 2016-04-20 天地未来(北京)科技发展有限公司 一种无烟煤富氧燃烧法资源化处理煤化工高盐废水的方法
WO2018182406A1 (fr) 2017-03-29 2018-10-04 Minplus B.V. Procédé de réduction de la corrosion d'un échangeur de chaleur d'un incinérateur comprenant ledit échangeur de chaleur

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HU228684B1 (hu) 2013-05-28
HUP0202095A2 (hu) 2004-06-28
DE10131464A1 (de) 2003-01-16
DE50211184D1 (de) 2007-12-27
EP1271053A3 (fr) 2003-05-02
DE10131464B4 (de) 2006-04-20
HU0202095D0 (fr) 2002-09-28
US20030065236A1 (en) 2003-04-03
PL354795A1 (en) 2002-12-30
JP4221194B2 (ja) 2009-02-12
ATE378554T1 (de) 2007-11-15
HUP0202095A3 (en) 2007-03-28
PL199924B1 (pl) 2008-11-28
ES2295258T3 (es) 2008-04-16
EP1271053B1 (fr) 2007-11-14
JP2003065522A (ja) 2003-03-05
DK1271053T3 (da) 2008-03-17

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