EP3377215A1 - Abscheidemittel für die behandlung von rauchgasen - Google Patents

Abscheidemittel für die behandlung von rauchgasen

Info

Publication number
EP3377215A1
EP3377215A1 EP16782247.7A EP16782247A EP3377215A1 EP 3377215 A1 EP3377215 A1 EP 3377215A1 EP 16782247 A EP16782247 A EP 16782247A EP 3377215 A1 EP3377215 A1 EP 3377215A1
Authority
EP
European Patent Office
Prior art keywords
agent
gases
capture agent
csh
capture
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.)
Withdrawn
Application number
EP16782247.7A
Other languages
English (en)
French (fr)
Inventor
Louis Masset
Bernard Somerhausen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Carmeuse Research and Technology
Original Assignee
Carmeuse Research and Technology
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 Carmeuse Research and Technology filed Critical Carmeuse Research and Technology
Publication of EP3377215A1 publication Critical patent/EP3377215A1/de
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/508—Sulfur oxides by treating the gases with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01D53/68—Halogens or halogen compounds
    • B01D53/685—Halogens or halogen compounds by treating the gases with solids
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    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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    • B01J20/0229—Compounds of Fe
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Definitions

  • the present invention relates to a solid capture agent for the treatment of flue gases and a method for preparing such an agent.
  • the present invention also relates to a process for treating flue gases by means of said capturing agent.
  • the gases are washed in an absorber using an aqueous suspension of a capturing agent.
  • the captured acidic compounds are recovered in the suspension at the outlet of the absorber in the form of reaction products, combined with the capturing agent.
  • the SO2 and SO3 captured are recovered in this suspension in the form of sulphites and / or sulphates.
  • aqueous suspension of a capture agent is injected into the absorber in the form of droplets.
  • the flow rate and the concentration of capturing agent in said suspension and the temperature of the gases to be treated are such that the water present in the suspension is evaporated and entrained by the gases.
  • the captured acidic compounds are recovered as reaction products in solid residues.
  • a third method of treatment called “dry process”
  • the gases are put in direct contact with a solid capturing agent, either by dry injection of said agent in the absorber or in a driven bed, or by maintenance of the agent in a fluidized bed. It is also possible to pass the gases through a fixed bed of a capturing agent.
  • the captured compounds are then present as reaction products in the solid residue.
  • calcium-containing compounds in a form capable of reacting with the acidic compounds are used as solid capturing agents.
  • SO2 is generally the most difficult to capture by chemical reaction because of its less pronounced acid character.
  • a basic capture agent that effectively captures SO2 captures a fortiori more acidic compounds such as HCI, H Br, H F and SO3. Therefore, the capturing agents can be evaluated by their ability to capture SO2 with the understanding that they also capture the other acidic compounds mentioned above. This approach is also adopted in the present description.
  • a first example of a known solid capturing agent is calcium hydroxide.
  • the reaction between Ca (OH) 2 and SO 2 present in the gases is favored by high humidity, such as that encountered, for example, in wet processes or in semi-wet processes.
  • high humidity such as that encountered, for example, in wet processes or in semi-wet processes.
  • Ca (OH) 2 An important disadvantage of Ca (OH) 2 is its pasty consistency in combination with a high relative humidity. This results in the formation of solid deposits in the installations and increases the risk of clogging, forcing the user to treat the gases under conditions of low relative humidity and therefore under non-optimal gas treatment conditions. The impasto of the grains of Ca (OH) 2 is all the more important as the porosity is lower.
  • Ca (OH) 2 agent present in the form of granules down to a very low level while it still contains a significant amount of Ca (OH) 2 which has not reacted with the compounds of the gas to be purified.
  • Ca (OH) 2 must be used in significant excess for the gas treatment, which also leads to a high amount of waste to be disposed of.
  • Other known solid capture agents are calcium silicate hydrates of formula (CaO) x (Si02) y (H20) z containing a variable quantity of free water.
  • DE-OS-3611769 it is proposed to use as a capturing agent a lime-rich hydrated calcium silicate granulate, as obtained from the concrete manufacturing process, this agent preferably having a high porosity. .
  • a calcium silicate hydrate or a calcium aluminate hydrate prepared by reacting an aqueous suspension containing an alkaline calcium compound (CaO or Ca (OH) 2) with a silica or an alumina.
  • WO 00/48710 discloses capturing agents comprising calcium silicates hydrated in a pre-tobermorite phase, having a Ca / Si molar ratio between 1 and 5, a molar ratio h O / Ca between 0, 1 and 2 and a particle size of between 0.5 and 30 mm.
  • the capturing agent is obtained from cristobalite and quartz. This type of product is manufactured in aqueous suspension and drying to obtain a dry product represents considerable costs. Goals of the invention
  • the object of the present invention is to overcome the disadvantages of capturing agents known from the state of the art and to provide a capture agent with improved efficiency comprising hydrated calcium silicate with molar ratios Ca / Si and Ca / h O in a narrow range and a particularly fine particle size.
  • the invention also proposes a method for producing the capture agent and a method for purifying fumes using the capture agent according to the invention. Summary of the invention
  • the present invention discloses a capture agent for the treatment of gases, having an active phase which comprises a hydrated calcium silicate of type (CaO) x (SiO 2 ) y (H 2 O) z with a Ca molar ratio. / If between 1.55 and 1.72, preferably between 1.65 and 1.72 and a molar ratio h 2 O / Ca of between 1 and 1.4, preferably between 1.1 and 1.3, "Z" being between 0.3 and 0.8, the capturing agent having a specific surface area greater than 120 m 2 / g, preferably greater than 150 m 2 / g and particularly preferably greater than 200 m 2 and a pore volume greater than 0.4 cm 3 / g, preferably greater than 0.6 cm 3 / g and particularly preferably greater than 0.8 cm 3 / g
  • the average particle size (D50) is less than 1000 ⁇ , preferably less than 500 ⁇ and particularly preferably less than 300 ⁇ ;
  • said agent further comprises sodium chloride, calcium chloride or iron chloride hydrated within its pores;
  • said agent further comprises a fluidizing agent selected from monoethanolamine, diethanolamine, triethanolamine, monoethylene glycol, diethylene glycol and triethylene glycol.
  • the invention also discloses a process for preparing a capture agent according to the invention characterized in that calcium silicate hydrate is obtained by: - preparation of an aqueous suspension of silica and lime, at the start colloidal silica of silica fume or diatomaceous earth;
  • the preparation of colloidal silica, silica fume or diatomaceous earth or a mixture of these ingredients comprises at least one of the following steps:
  • chlorine salt preferably sodium chloride, calcium chloride or iron chloride.
  • the invention also discloses a gas treatment process by contacting the capture agent according to the invention with the gases to be treated.
  • the gas treatment process consists of a dry process, in which the gases are brought into direct contact with the capture agent where the gas to be treated preferably passes through.
  • an electrostatic precipitator or bag filter containing this agent preferably contains this agent.
  • the effectiveness of the capture agent according to the invention is evaluated by measuring the concentration of SO 2 as an indicator compound, in the gases at the outlet of the electrostatic precipitator or bag filter, and replacing the capturing agent when the concentration exceeds a previously fixed limit value.
  • the object of the present invention is to provide a capture agent based on calcium silicate hydrate (CSH) or a composition containing hydrated calcium silicate in the form of powder for the treatment of fumes as well as a method of manufacturing this product.
  • CSH calcium silicate hydrate
  • the invention also discloses a method for purifying fumes using the capture agent of the present invention.
  • the hydrated calcium silicates are generally characterized by the CaO / SiC> 2 and H20 / CaO molar ratios and by its structural characteristics such as its microstructure ( ⁇ , ⁇ or ⁇ -type CSH), its Ca (OH) 2, the stability of molecular water, its pore volume (VP), pore size, specific surface area (BET) and CO2 content.
  • the low CO2 capture capacity is a much sought-after property since the gases to be purified are generally combustion gases that are much more loaded with CO2 than in SO2 or HCI, for example (10% of CO2 compared with 0.2% of CO2). SO2 for example).
  • Certain properties are also obtained in certain synthesis conditions involving T °, time, pressure and additives used.
  • the particle size of CSH according to the invention should not exceed on average (D50) and measured in volume, 1000 ⁇ , preferably 500 ⁇ and particularly preferably 200 ⁇ .
  • the particle size measurements are made by laser diffraction where all the particles are assimilated to spheres.
  • the device used is the Sympatec HELOS / K sensor according to the Fraunhofer method.
  • a particularly advantageous way of preparing the CSH is to replace 2 to 4%, preferably about 3% of the silica with freshly prepared colloidal silica. To do this, a dilute acid (H 2 SO 4, HCl, etc.) is reacted with a solution of sodium silicate. This procedure is referred to as the "amplified method" according to the present invention.
  • Fresh colloidal silica used in small amounts (1 to 5%) in the silica mixture increases the BET up to 200 m 2 / g and a pore volume VP> 0.5 cm 3 / g.
  • the pore volume is measured according to the BJH method (Barrett-Joyner-Halenda).
  • the "Ca” represents only the calcium content that can react with the silica. If one of the reagents (lime or silica) contains calcium carbonate which does not participate in the hydrothermal synthesis of HSC, this calcium is not taken into account for the calculation of the Ca / Si ratio. This calcium carbonate is determined by thermogravimetry.
  • the CSH gels comprise water in three different forms:
  • thermogravimetric analysis of such a product When a thermogravimetric analysis of such a product is carried out, four zones are distinguished:
  • the Ca ⁇ 3 is decarbonate, which can have three origins:
  • the water is supplied by the fumes and condenses preferentially by capillary effect in pores.
  • the water is already in the pores from the manufacture of the porous solid and the Ca (OH) 2 is already dissolved there ready to react with the acid gases.
  • a chloride salt during the synthesis of HSC for example sodium chloride, calcium chloride or iron chloride
  • chlorine forms hydrated calcium chlorides in the pores which gradually release water from the water. Crystallization when in contact with hot gases. They thus release water available for the dissolution of acid gases.
  • CaCl 2 .6H 2 O stable below 30 ° C.
  • CaCl 2 2.4 H 2 O stable from 30 to 45 ° C.
  • the following table compares the effectiveness of different capture agents tested incinerator.
  • the specific surface area (BET - Brunauer-Emmett-Teller) of the powders is measured according to the IS09277 standard, second edition of the 1st September 2010.
  • the calculation of the porous distribution is based on the stepwise analysis of the adsorption branch of the isotherm by the BJH method, by Barrett, Joyner and Halenda (1951), conventionally used with nitrogen at 77K as an adsorbent gas. The method is described in DIN66134.
  • CSH The reaction of capturing pollutants such as sulfur oxide with CSH releases the silica and the water of constitution of CSH. Only the lime present in the CSH molecule reacts with the pollutant. CSH therefore has the disadvantage of having a larger amount of material not participating in the pollutant catching reaction than calcium hydrate. However, this disadvantage is largely offset by the greater reactivity of the CSH with respect to the pollutant because of its large specific surface area and its high pore volume.
  • the CSH according to the invention contains more alkalinity accessible per 100 kg of product and therefore generates less waste per kg of SO2 captured; which is a great advantage because landfill costs are less important.
  • the synthesis of HSC can be at atmospheric pressure at about 95 ° C for about 3 hours, or at high pressure (between 5 and 10 bar, corresponding to saturated vapor temperatures between 150 and 180 ° C). As the synthesis times are shortened under these conditions (approximately 30 minutes), the synthesis can be done in "batch" mode, or continuously in a reactor of the coil type thermostatized or simply insulated against heat loss.
  • the synthesis of the colloidal silica is carried out by reacting dilute sulfuric acid with sodium silicate in solution. A few minutes are waited for the colloidal silica to precipitate to form a milky suspension. Then, the amorphous silica (diatomaceous earth, silica fume, ...) and the quicklime are introduced to carry out the synthesis of the CSH suspension.
  • the purpose of the drying is to reduce the moisture content of the capture agent from approximately 78% of free water to 5-20% of free water in order to obtain a powder capture agent having adequate flow properties.
  • the calories can be obtained by burning a fossil fuel or by recovering lost calories (lime rotary kilns without preheater, cement kilns, etc.) via a heat exchanger.
  • the calories can be transported by:
  • a "breakthrough time" is defined as the time for the concentration of bed exit pollutants to be equal to the concentration of pollutants entering the bed. This piercing time is the image of the performance of the capturing agent.
  • the bag filter makes 35 m 2 of filtering surface, ie 12 rows of 5 sleeves per row.
  • a sleeve thus makes 0.58 m 2 of lateral surface, 0.58 m of perimeter and 1 m of length.
  • the capturing agent is sent continuously on the sleeves and the twelve rows of sleeves are regularly beaten with compressed air, row after row, with an adjustable cycle time of 30 to 60 minutes.
  • the flue gas filtration rate is 1 m / minute and the recomposed flue gas flow can be adjusted according to the filtration temperature to respect this speed.
  • the CSH milk synthesis was carried out in a laboratory PA reactor. The synthesis of HSC was done for three hours at different temperatures. In the case of amplified CSH, 3% of fresh colloidal silica was added during the synthesis.
  • Cekesa diatomite (Spain) was used with a specific surface area of 103 m 2 / g and a pore volume of 0.29 cm 3 / g containing 72% SiO 2 ; 27.2% of CaCO 3 and 0.8% of (Al 2 O 3 + MgO).
  • Examples 1 to 6 are carried out with a Ca / Si ratio of 1.7; examples 7 to
  • the performance of CSH according to the invention was compared with Ca (OH) 2.
  • the synthesis conditions of CSH are those carried out at 150 ° C. and 5 bar for three hours.
  • the CSH milk was then dried in an atomizer without direct contact with the fumes of the hot air generator operating on natural gas. 15% residual water remained after drying.
  • the words "kg acid” means total weight of SO2 and HCI.
  • Type of capture agent 2 kg agent per 3 kg agent 4 kg agent kg acid per kg acid per kg acid

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EP16782247.7A 2015-11-16 2016-10-18 Abscheidemittel für die behandlung von rauchgasen Withdrawn EP3377215A1 (de)

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BE2015/5744A BE1023623B1 (fr) 2015-11-16 2015-11-16 Agent de captation pour le traitement des fumées
PCT/EP2016/074961 WO2017084822A1 (fr) 2015-11-16 2016-10-18 Agent de captation pour le traitement des fumees

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DE2902108C2 (de) * 1979-01-19 1983-11-24 Mars Inc., 22102 McLean, Va. Verwendung von Calciumsilikatgranulaten beziehungsweise -pulvern
US4707270A (en) * 1985-01-31 1987-11-17 Ube Industries, Ltd. Process for treating waste water containing phosphorus compounds and/or organic cod substances
DE3611769A1 (de) 1986-04-08 1987-10-15 Ytong Ag Verfahren und vorrichtung zur reinigung von abgasen
US4804521A (en) 1986-11-07 1989-02-14 Board Of Regents, The University Of Texas System Process for removing sulfur from sulfur-containing gases
US5100643A (en) 1988-03-02 1992-03-31 Board Of Regents, The University Of Texas System Processes for removing acid components from gas streams
US5401481A (en) 1986-11-10 1995-03-28 Board Of Regents, The University Of Texas System Processes for removing acid components from gas streams
US6676911B1 (en) * 1998-07-23 2004-01-13 Sumitomo Osaka Cement Co., Ltd. Exhaust gas treating agent, process for producing the same, and method of treating exhaust gas
WO2000048710A1 (fr) * 1999-02-17 2000-08-24 Carmeuse S.A. Agent de traitement de gaz, procede de preparation de cet agent, et procede de traitement de gaz au moyen de cet agent
EP1235758B1 (de) * 1999-08-26 2005-11-30 Vijay Mathur Multiphasige calsiumsilikathydrate, verfahren zur herstellung derselben und verbesserte papier- und pigment-produkte diese enthaltend
US6726807B1 (en) * 1999-08-26 2004-04-27 G.R. International, Inc. (A Washington Corporation) Multi-phase calcium silicate hydrates, methods for their preparation, and improved paper and pigment products produced therewith
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US7048900B2 (en) * 2001-01-31 2006-05-23 G.R. International, Inc. Method and apparatus for production of precipitated calcium carbonate and silicate compounds in common process equipment
NZ539746A (en) * 2002-11-05 2008-03-28 James Hardie Int Finance Bv Method and apparatus for producing calcium silicate hydrate
EP2463317A1 (de) * 2010-12-09 2012-06-13 BASF Construction Polymers GmbH Additiv für fließmittel enthaltende Baustoffmischungen
WO2015171745A1 (en) * 2014-05-06 2015-11-12 William Marsh Rice University Shape-controlled cement hydrate synthesis and self-assembly

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BE1023623A1 (fr) 2017-05-18

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