PROCESS FOR THE CLEANING OF GASEOUS EFFLUENTS BY SELECTIVE REMOVAL OF THE POLLUTANTS CONTAINED THERE

专利摘要:
The gaseous effluent to be purified is analyzed to identify the pollutants it contains, and then the following successive operations are conducted, according to the pollutants identified: at least partial, advantageously complete, elimination of tars, at least partial elimination, advantageously complete, non-methane volatile organic compounds (NMVOCs); at least partial, advantageously complete, elimination of the halogenated compounds; at least partial removal of at least one of H 2 S, NH 3, SO 2, CO 2 and NOx by choosing from: at least partial removal of at least one of H 2 S , NH3, SO2 and CO2 by passing the gaseous effluent through chilled water; or at least partial removal of H2S in the case where CO2 is co-present with it, by bubbling the gaseous effluent into a liquid allowing the chemical absorption of H2S, or at least partial removal of NOx by bubbling of the gaseous effluent in a liquid for the chemical absorption thereof; or elimination in any order of: H2S alone or with CO2; CO2 alone or SO2 alone or SO2 + CO2; and NOx alone.
公开号:FR3018461A1
申请号:FR1452024
申请日:2014-03-11
公开日:2015-09-18
发明作者:Brahim Abdelkader Ben
申请人:Brahim Abdelkader Ben；
IPC主号:

专利说明:

[0001] The present invention relates to the field of the purification of gaseous effluents, and relates, in particular, to a process for the purification of contaminated gaseous effluents. DETAILED DESCRIPTION OF THE INVENTION . The contaminated gaseous effluents are characterized by the diversity and complexity of the nature of the pollutants and by their variable and fluctuating concentrations of one gaseous effluent to another, or even within the same effluent. The usual / conventional methods of effluent depollution encounter major and even impassable difficulties for the treatment of these effluents, since only one mode or one treatment technique is incapable of treating both the entire process. pollutants present in the gaseous effluent. Among the pollutants whose treatment proves to be extremely difficult, especially by a single mode or a single technique, mention may be made especially of: tars, hydrogen sulphide (H2S), non-volatile non-methane organic compounds (NMVOCs), in particular in particular the silanes and siloxanes present therein. The aim of the present invention is to propose a method for purifying gaseous effluents polluted by at least one pollutant chosen from tars, NMVOCs, halogenated compounds, hydrogen sulphide (H 2 S), organic sulphides including mercaptans, ammonia (NH3), sulfur dioxide (SO2), nitrogen oxides (N0x) and carbon dioxide (CO2), the CO2 removal being more or less advanced depending on the desired quality for the gaseous effluent.
[0002] The gaseous effluents to be treated are in particular synthesis gas, biogas, natural gas, gases associated with the extraction of petroleum and industrial gaseous discharges. Tars are very specific compounds of condensable hydrocarbons, mainly including polycyclic aromatic hydrocarbons (PAHs) and phenols. Tars represent not only a health risk but also a real embarrassment and a serious constraint for the proper functioning of gasification equipment and installations. They condense easily on cold spots and induce problems of wear and corrosion of the installations and less efficient heat exchanges. In addition, tars can form coke by coking or soot by polymerization. All these deposits are at the origin not only of the clogging of the pipes or the installations but also of the deactivation of the catalysts. NMVOCs consist of carboxylated and carbonyl volatile organic compounds (VOCs) such as volatile organic acids, alcohols, aldehydes and ketones as well as silanes and siloxanes. The halogenated compounds are pollutants that may exist in the composition of the gaseous effluent and may contain the chemical elements: fluorine, chlorine, bromine, iodine. The organic sulphides are in particular CSH, CS2, COS and the mercaptans, namely the RSH compounds, R being a hydrocarbon radical, the mercaptans being generally in the solid state.
[0003] The main standard techniques for the desulphurisation (removal of H2S) of gaseous effluents include biological treatment, chemical absorption, activated carbon adsorption, the membrane permeation process, pressure-modulated "PSA" processes, cryogenics and incineration (or thermal oxidation): - the biological treatment by bacteria with all its variants has the major disadvantages of occupying a very large area, a high investment cost and a very complex management of the fact requirements and fragility of bacteria; the absorption or chemical washing, whether acidic or basic, has the major drawbacks of pollution displacement phenomenon and complex management of sludge treatment resulting from the washing; - Activated carbon adsorption has the major drawbacks of being very limited vis-à-vis the concentration and types of pollutants that can be treated; the management of pollutant-saturated coal is also quite complex; and the membrane permeation process, the PSA processes, the cryogenics and the incineration are energy-consuming, expensive processes which are limited in their field of action and very difficult to implement. Nitrogen oxides (N0x) are oxidized forms of nitrogen. NO, NO2, N20, N204 and N203 are generally referred to herein as the generic term "NOx". Gaseous ammonia (NH3) can be found among the components of gaseous effluents resulting from the purification of wastewater or industrial discharges.
[0004] In some cases, CO2 must be removed at least partially, for example in the treatment of biogas. Synthesis gas or syngas is a combustible gas mixture produced by thermochemistry. It contains mainly water vapor, hydrogen, methane, carbon monoxide and a little carbon dioxide as well as thermolysis residues whose composition and quantity vary according to its production method and according to the carbon source (eg wood or coal) that was used to produce it. Almost all these residues are toxic, carcinogenic or mutagenic compounds. In particular, the synthesis gas must be purified in order to eliminate the tars it contains. It may also contain NMVOCs, halogenated compounds, hydrogen sulphide, organic sulphides. It can also contain moisture and must be dried. Biogas is the gas produced by the fermentation, also known as anaerobic digestion, of animal or plant organic matter in the absence of oxygen. This fermentation occurs naturally in marshes for example or spontaneously in landfills containing organic waste or is artificially caused in digesters for example to treat sewage sludge, industrial or agricultural organic waste. Biogas is a mixture composed essentially of methane (typically 40 to 70% by volume) and carbon dioxide with varying amounts of water vapor and hydrogen sulfide (H2S) as well as NMVOC compounds. It may also contain organic sulphides and NH3. So it contains moisture, it must also be able to be dried. In the case of biogas produced mainly by sewage treatment plants and landfills, the main problem is the emanation of odors, and mainly H2S which generates olfactory nuisances, also degrades equipment and works and presents health risks for staff and neighboring populations.
[0005] Biogas upgrading of biogas also requires the removal of CO2 and moisture to a quality similar to that of natural gas (around 98% by volume of methane). The purification techniques are multiple but the production of biomethane is only in its beginnings in Europe, which counts only a few hundred installations. Natural gas is a fossil fuel composed of a mixture of naturally occurring hydrocarbons in porous rocks in gaseous form. The most exploited form of natural gas is conventional gas not associated with oil extraction, which includes gas besides methane and a variable rate of heavier hydrocarbons, carbon dioxide, H2S, SO2, organic sulphides. It also contains moisture and must be dried. The gases associated with the extraction of oil are the gases present in solution in the oil. They are separated during the extraction of the latter. They are conventionally called "APG" or flaring gas. Their composition is quite similar to that of biogas with variable concentrations of pollutants to be eliminated: H2S, SO2, organic sulphides, NMVOC, CO2. They also contain moisture and must be dried.
[0006] Industrial gaseous discharges consist of all types of air pollutants resulting from human activities and generated directly or indirectly in the atmosphere and confined spaces in the form of substances with harmful consequences likely to endanger human health, to harm the resources and ecosystems, to influence climate change, to damage material assets, to cause excessive odor nuisance. They can be of various natures: H2S, SO2, NH3, NOM. organic sulphides, NMVOCs, Therefore, a new purification mode qualified as ecological, energy-saving, not complex in terms of installation and management and having the faculty of treating all types of pollutants, can be considered as a revolution in the field of purification of polluted gaseous effluents.
[0007] The present inventor proposes a modular process comprising different treatment modules, each being intended for a specific treatment, such as the elimination of tars, NMVOCs, halogenated compounds with drying, NOMs, the elimination of H2S with, where appropriate CO2 and NH3, recovery of the eliminated H2S, etc., and in particular in the case of biogas, the enrichment in methane of the purified biogas up to the production of biomethane. Depending on the composition of the gaseous effluent to be purified, some of these modules are combined with one another so as to propose the most efficient solution. This modularity also makes it possible to selectively remove the pollutants present in the gas and to find them the optimal recycling or recovery solution in terms of cost and environmental impact. In addition, the efficiency of the process does not depend on factors that are difficult to control, such as pressure, humidity, temperature, instantaneous variations in the volume of the gaseous effluent to be treated and / or the pollutant load. Whether it concerns the purification of biogas at the sewage treatment plant, the discharges or the associated burned gases, the method of the invention can advantageously use three different models of modular solution for specific desulfurization (elimination of H2S), which also enriches methane in biogas purified by partial or total removal of CO2 to produce biomethane with installation costs, treatment and energy needs never approached to date. The more the gas is contaminated with contaminants, the more the gap between the existing solutions and the method of the invention is widening.
[0008] Moreover, treatment reagents according to the invention are advantageously transformed during these treatments into new non-harmful and / or value-added products which can serve as basic raw materials in industrial activities.
[0009] Whether for biogas, synthesis gas, natural gas or associated gases, the quality of the purified gaseous effluent is perfectly compatible with the totality of the energy recovery solutions and consequently allows, according to the quantities of effluent recovered gas and existing industrial and / or gas network infrastructure, to value it in: - electricity: direct supply of engines or high-efficiency gas turbines (CCGT) or fuel cells with biogas and natural gas synthesis; this valuation is the simplest to implement and a particularly interesting solution for local electrical needs (in regions that do not yet have access to electricity); biomethane: can be used as fuel or for reinjection into the natural gas distribution network (after THT odorization); natural gas: depending on the availability of transport infrastructure, it will be: injected directly into the natural gas distribution network (transport by pipeline); liquefied (LNG or LPG) for transport by boat; - converted into marketable GTL (Gas to Liquid) fuel, methanol, olefins, DME (dimethyl ether), ammonia. Whatever its configuration, the method of the invention does not generate any harmful discharge into the atmosphere, no water pollution (closed circuit operation), no soil pollution (recovery of eliminated pollutants in non-toxic and value-added products not requiring burial). The method of the invention proposes an innovative gaseous effluent purification technology, efficient, ecological and economical particularly well suited to the treatment of synthetic gas loaded with tars and H2S. Its operation and its treatment efficiency are not affected by the volume of the gaseous effluents to be treated, the pollutant load or their respective variations. Thanks to its modular concept and innovative and exclusive processing techniques, the process of the invention makes it possible to selectively eliminate the different pollutants contained in the raw gaseous effluent and to find them the optimal recovery solution in terms of costs and energy. 'environmental impact.
[0010] Desulphurization is primarily aimed at the removal of H2S and, in some cases, SO2. The H2S removed from the gaseous effluent is advantageously recovered directly on site in two non-toxic and value-added by-products.
[0011] The removed (carcinogenic) NMVOCs are used as fuel with a high calorific value while the organic sulphides are removed by filtration through a filter medium. The present invention therefore firstly relates to a process for purifying a gaseous effluent containing pollutants chosen from tars, non-methane volatile organic compounds (NMVOCs), halogenated compounds and hydrogen sulfide (H2S). , ammonia (NH3), sulfur dioxide (SO2), nitrogen oxides (NOx) and carbon dioxide (CO2), characterized in that the gaseous effluent to be purified is analyzed for identify the pollutants it contains, then conduct the following successive operations according to the pollutants identified: (1) at least partial, advantageously complete, removal of tars by cooling the raw gaseous effluent to pass the tars from their gaseous state to their liquid state and physical separation thereof to recover a treated gaseous effluent; (2) at least partial, advantageously complete, removal of the NMVOCs by bubbling the gaseous effluent into a liquid mixture of NMVOCs of the same composition as that of the NMVOCs present in the gaseous effluent to be treated so that the NMVOC gases condense and join said liquid mixture, and recovering the gaseous effluent treated; (3) at least partial, advantageously complete, elimination of the halogenated compounds by bubbling the gaseous effluent into a salification solution, the salification allowing simultaneous drying of the gaseous effluent, and recovery of the treated gaseous effluent; (4) at least partial removal of at least one of H2S, NH3, SO2, CO2 and NOx by selecting from: (4a) at least partial removal of at least one of H2S, NH3, SO2 and CO2 by passing the gaseous effluent into chilled water in which said gaseous H 2 S, NH 3, SO 2 and CO2 are trapped in this state by physisorption, the process water being saturated with said gaseous pollutants being separated to obtain a treated gaseous effluent; or (4b) at least partial removal of H2S in the case where CO2 is co-present with it, by bubbling the gaseous effluent into a liquid allowing the chemical absorption of H2S with simultaneous removal of at least a part of the CO2, or at least partial NOx removal by bubbling the gaseous effluent into a liquid for chemical absorption thereof, and recovering the treated chemical effluent; or (4c) elimination in any order of: - H2S alone or with CO2 by spraying in a stream of the gaseous effluent of a reagent able to combine with respectively H 2 S or H 2 S + CO2 to give a reaction product solid which is removed from the gaseous effluent to recover it in the purified state; - SO2 alone or CO2 alone or SO2 + CO2 by humidification of the gaseous effluent, then spraying in the humidified gaseous effluent of a reagent capable of combining with the reaction product between the humidifying water and respectively SO2 or CO2 or SO2 + CO2 to give a final reaction product that is removed from the gaseous effluent to recover it in the purified state; and - NOx alone by reaction of the gaseous effluent with H 2 O 2 and then spraying in the gaseous effluent thus treated with a reagent capable of combining with the reaction product between H 2 O 2 and NOx to give a final reaction product which the gaseous effluent is removed to recover it in the purified state.
[0012] The gas to be treated is advantageously chosen from natural gas, gases associated with the extraction of petroleum, biogas, synthesis gases and industrial gaseous discharges. In (1), the gaseous effluent to be degassed can advantageously be passed through at least one vertical tube-bundle heat exchanger, connected at its base to a tars collector, said gaseous effluent passing outside the tubules and a cooling fluid passing inside the tubules, the tars liquefying along the tubules to flow gravitarily and be collected in the collector.
[0013] In particular, according to a particular embodiment, two tubular bundle heat exchangers (E2, E2 ') are used, connected at their base to a tars collector and a third heat exchanger (E1) of the same type but without tar collector and the effluent gas is passed through the following two successive sequences: - in the first sequence, the effluent gas is passed at a temperature T1 greater than 120 ° C in a first exchanger with collector (E2 ') without heat exchange, then in the heat exchanger without collector (El) where it undergoes heat exchange to cool it to the temperature T2 of 120 ° C + 2 ° C, then in the other heat exchanger with collector (E2) for cooling to a temperature T3, in particular 25 ° C, the tars being retained in the walls of said exchanger (E2) outside its tubules, the tapped gas exiting said exchanger E2; and in the second sequence, the gaseous effluent which continues to arrive at the temperature T1 is no longer passed in the exchanger E2 'but in the exchanger E2 without subjecting it to heat exchange, causing the fluidification of the tars. retained in it, which then flow and can be collected in the associated collector (6), then in the collectorless heat exchanger (El) where it undergoes heat exchange to cool it to a temperature T2 of 120 ° C + 2 ° C, then in the other heat exchanger with collector (E2 ') to cool it to a temperature T3 of 25 ° C, the tars being retained in the walls of said exchanger E2' outside its tubules, the tapped gas leaving said exchanger E2 '; then that the cycle E2'-El-E2 and then E2-E1-E2 'is repeated as long as it arrives from the gaseous effluent. In (2), the gaseous effluent to be treated can advantageously be passed through an overflow column (C1) with cooling coil, containing said liquid mixture, maintained at a temperature of -10 ° C + 2 ° C, the bubbling in said column C1 for removing NMVOCs from the gaseous effluent to be treated by the phenomenon of condensation. In (3), the gaseous effluent to be treated can be advantageously bubbled through an overflow column (CH) filled with an acid solution, such as sulfuric acid as salification solution, bubbling into said solution. for eliminating halogenated compounds present in said gaseous effluent together with traces of water if they exist. In (4a), the separated process water, saturated with the said gaseous pollutants and which may also contain pollutants in the solid state, is advantageously sent to a separation reactor, on the one hand, water charged with the possible pollutants solid and, on the other hand, gas, the water, if it is loaded with solid pollutants, then being filtered to remove these pollutants and advantageously recycled to the stage (4a). In (4a), in particular for the removal of H 2 S, the gaseous effluent to be treated can advantageously be passed through desulfurization columns (C2 to C7) filled with chilled water at a temperature of between 2 ° C. C and 5 ° C, constituting a desulphurization stage, said water, by an H2S absorbing physisorption phenomenon in the ratio 1 L of water to 4 L of H2S, the process water loaded with gaseous pollutants and possibly sulphides solid organics being sent to a water / gas separation reactor, then the water separated during this degassing if it is loaded with organic sulphides, being treated by filtration and reinjected as treated water into the desulfurization stage.
[0014] The desulfurization columns are advantageously arranged in two series connected in parallel, each series comprising three columns connected in series, the columns of the two series (C2-C3-C4) being in turn in desulphurization service and in regeneration service. process water. The gas separated at the level of the liquid / gas separation reactor can advantageously be sent to a reactor containing an acid solution, such as acetic acid, for converting the H 2 S and at least a part of the CO2 present in the gas. , the carbon and the sulfuric acid solution obtained being sent to storage tanks and the possible fraction of unreacted CO2 being released into the atmosphere. In the filtration step, the separated liquid is advantageously passed through one or more filters (Fia, Fib) with a substrate such as activated carbon, the various filters advantageously being connected in parallel for an alternating operation in the case where the one is saturated, to capture solid state pollutants, such as organic sulphides, then in at least one filter F2, F3, F4 in series to remove the remaining fine impurities, and then in a water osmosis unit to obtain quality water advantageously reinjected to the desulphurization stage.
[0015] In (4b), the effluent to be purified is advantageously bubbled in a series of overflow columns at room temperature, the overflow columns (C8, C9 and C10) containing an acid solution, such as acetic acid, for transforming the H2S and the CO2 present in the gas, the carbon and the sulfuric acid solution obtained being sent to recovery tanks, and the at least partially desulphurized gaseous effluent being recovered at the outlet of the last column. In (4b), the effluent to be purified is bubbled through a series of overflow columns at room temperature, the overflow columns (C8, C9 and C10) containing a solution of oxygenated water for conversion of NOx present in the reactor. gas, the HNO3 obtained being sent to a recovery tank, and the gaseous effluent at least partially freed of nitrogen oxides being recovered at the outlet of the last column.
[0016] In (4c), the effluent is advantageously diffused in an upflow stream in a reactor comprising, in its lower part, a device, such as a ramp, for supplying water or H2O2 solution when a humidification or a reaction with H 2 O 2 is respectively provided, in its upper part, a device, such as a ramp, reagent spraying, and, in the lower part, a device for recovering the end products of reaction, the reagents applied being in particular Cu (OH) 2 in the case of removal of H2S alone; Ca (OH) 2 in the case of the removal of H2S + CO2; of Ca (OH) 2 in the case of removal of CO2 alone by reaction of H2CO3 resulting from the reaction of CO2 + H2O with Ca (OH) 2; of Ca (OH) 2 in the case of removal of SO2 alone or SO2 + CO2 by humidification followed by treatment with Ca (OH) 2; of Ca (OH) 2 in the case of removal of NOx alone by reaction with H 2 O 2 and then by chemical absorption of HNO 3 on Ca (OH) 2.
[0017] To better illustrate the object of the present invention, will be described below, by way of indication and not limited to several particular embodiments with reference to the accompanying drawing.
[0018] In this drawing: - Figure 1 shows schematically an evaporation module of a gaseous effluent; - Figures 1.1 and 1.2 illustrate the two initial sequences operating alternately of the passage of the gaseous effluent through the module of Figure 1, these two sequences repeating in turn thereafter; FIG. 2 diagrammatically represents a compression module for the gaseous effluent at the outlet of the module of FIG. 1; FIG. 3 schematically represents a module for eliminating NMVOCs by condensation; - Figure 4 shows schematically a module for removing halogenated compounds by salification with drying; - Figure 5 schematically shows a physisorption desulfurization module; - Figure 6 schematically shows a liquid gas separation module (Reactor 1) and recovery of H2S by chemical absorption of H2S H2504 (Reactor 2); Figure 7 schematically shows a module for treating treated water; FIG. 8 schematically represents a purification module by chemical absorption of either H2S or NOx; Figure 9 shows schematically a purification module of different pollutants remaining after passing through the modules of Figures 3 and / or 4; and Figure 10 is a flowchart indicating the sequence of modules that can be used for purifying gaseous effluent. A more detailed description will follow, by way of example, of the different successive modules for implementing the method of the present invention. As indicated, these modules are commissioned according to the nature of pollutants of a gaseous effluent to be purified. In this description, temperature values that have been used for the purification of synthesis gas have been indicated. The complete elimination of the tars and the results expected for the elimination of the other pollutants have been achieved by implementing the different pathways shown diagrammatically in FIG. 10. DEGROUDRONNAGE MODULE OF A GASEOUS EFFLUENT - FIGS. 1, 1.1 and 1.2 Apparatus This module comprises three vertical tube heat exchangers E1, E2 and E2 ', hereinafter referred to as "tubular exchangers", two aerator refrigerators AR1 and AR2, two circulation pumps P1 and P2 and two fans S1 and S1'. . In the tubular exchangers E1, E2 and E2 ', the gaseous effluent to be treated circulates outside the tubes or tubules, cooling fluid flowing inside them. The tubular exchangers E2 and E2 'are equipped at the bottom with a tars collector. The closed circuit of the cooling fluid of the exchanger E1 is designated by the reference numeral 1. The closed cooling circuit of the exchangers E2 and E2 'is a common circuit designated by the reference numeral 2. The cooling fluid contained in the tubes or tubules of the exchangers is advantageously a solution of water and ethylene glycol, also called glycoled water. The aerator refrigerator AR1 is a plate-type heat exchanger in which the cooling fluid that has been heated is cooled by air. The aerator refrigerator AR2 is a plate-type heat exchanger in which the cooling fluid which has been heated is cooled by a mixture of air and water under pressure (misting mixture). It comprises preferably corrugated parallel plates 30, arranged in groups of two, the cooling fluid passing between the two plates of each group, which are bombarded on their outer faces by jets of water + air under pressure (misted water). The use of mist water reduces water consumption as well as energy consumption, the water being pressurized in air thanks to an integrated compressor and the water under pressure cooling directly without require refrigeration. In the tubular exchanger E1, the gaseous effluent to be cooled enters the upper region of the tubular bundle outside the tubules, and in the closed circuit 1, the cooling fluid at a temperature T7 is brought to the lower part in the tubules by the circulation pump P1 and leaves in the upper part at a temperature T8 to be cooled in the aero-refrigerator AR1 in order to be returned to the pump P1. The closed circuit 2 for cooling the tubular exchangers E2 and E2 ' comprises an upper branch 2a for the cold cooling fluid at temperature T5, a lower branch 2b for the cooling fluid heated to temperature T6 and a branch 2c which joins the two branches 2a and 2b and in the path 20 of which are the circulation pump P2 and the aerator-refrigerator with misting device AR2, which uses air cooled by water arriving via the pipe 3. The tubular exchangers E2 and E2 'are al at the top they are cooled with T5 fluid cooled in the aerator refrigerator with fogger AR2, the inlet of the fluid at temperature T5 being governed by valves 4 and 4 ', respectively. The fluid heated to temperature T6 exits at the bottom of each of the exchangers E2 and E2 ', to be addressed to the circulation pump P2. On each of these outlets, a non-return valve 5 and 5 'respectively are arranged.
[0019] The exchangers E2 and E2 'each have at the bottom a tars recovery collector respectively 6 and 6', the tars recovered in each of these collectors exiting through a pipe 7 and 7 'respectively, on which a valve 8 and 8 are respectively disposed. . The raw gaseous effluent at temperature T1 is fed to the lower part of each exchanger E2 and E2 ', above the associated tar recovery collector 6, 6', respectively via line 9 on which a valve 10 is located and by a bypass 11 of the pipe 9 which starts from a point upstream of the valve 10 and in the path of which is a valve 12. The gaseous effluent thawed out at the top of each exchanger E2, E2 'at temperature T3 and is sent by a pipe respectively 13, 13 'in the path of which the fan S1 and S1' respectively is located in a first branch 14 which is provided with non-return valves 14a and 14b and which comprises a bypass 15 for sending off the gaseous effluent tapped at temperature T3 towards the top of the tubular exchanger E1, gaseous effluent that leaves at the bottom of the exchanger E1 at the temperature T2 by a pipe 16 which is connected to the pipe 9 with the interposition of a valve 18 and which comprises a bypass 17 which starts from a point upstream of the valve 18 and in the path of which is a valve 19, to be connected to the pipe 11. The gaseous effluent therefore enters the lower part of each exchanger tubular E2, E2 'and spring at the top of the respective tubular exchanger E2, E2' through the pipe 13, 13 ', in the path of which the fan is respectively S1 and S1', to be addressed in the first branch 14 as described above or in a second branch 20 which is provided with nonreturn valves 20a and 20b respectively and which comprises a bypass 21 by which the gaseous effluent gaseous at temperature 14 will exit to be addressed to the module which will be described with reference to FIG. 2. Operation First initial sequence (FIG. 1.1) The raw gaseous effluent, in particular a synthesis gas, is injected at the temperature T1 via the pipes 9 and then 11 into the lower part of the exchanger E2 ' from which it emerges in the upper part, still in the raw state, through the pipe 13 'to be addressed via the lines 14 and 15 in the exchanger El. During the passage in this exchanger E2', the gaseous effluent does not undergo heat exchange. In the exchanger E1, the gaseous effluent is brought back to the temperature T2 and therefore leaves the lower part of the exchanger E1 at the temperature T2. The raw gaseous effluent stream is then discharged to the exchanger E 2 where it undergoes a heat exchange allowing the lowering of the temperature of the gaseous effluent to the temperature T 3 and the deposition of tars on the outer walls of the tubules of the exchanger E2.
[0020] The tars are retained in the walls of the exchanger E2 outside the tubules. At the outlet of the exchanger E2, the gaseous effluent cooled, freed of its tars, is at a temperature 14 greater than T3 after passing through the Si blower. Repetitive cooling of the gaseous effluent in the exchanger E2 would generate the clogging of this exchanger. For this reason, an alternating cooling with the exchanger E2 'is provided.
[0021] Second initial sequence - Figure 1.2 As just indicated, to prevent clogging of the exchanger E2, the raw gaseous effluent is fed through line 9, at the temperature Tl, through the exchanger E2, arriving at the bottom, without heat exchange, causing fluidification and not evaporation - tars already retained on the exchanger E2 in the previous sequence. This fluidification allows the flow of the latter to be recovered by the collector 6.
[0022] The raw gaseous effluent in the upper part of the exchanger E2 still leaves the raw state via the lines 13, 14 and 15 to the exchanger E1. In the exchanger E1, it undergoes a heat exchange leading to cool to the temperature T2. It is then returned to the exchanger E2 'through line 11 to undergo a second cooling where the tars are retained on the walls of the exchanger E2' outside the tubules, the raw gaseous effluent stream undergoing exchanger E2 'a heat exchange allowing the lowering of its temperature to the temperature T3 and the deposition of tars on the outer walls of the tubules of the exchanger E2'. At the outlet of the exchanger E2 ', the gaseous effluent cooled, freed of its tars, is at temperature 14 after passing through the fan S1'.
[0023] Repetition of the sequences of FIGS. 1.1 and 1.2 The alternation of these two sequences is repeated indefinitely as long as the gaseous effluent to be treated arrives, the tars then being deposited in the collector 6 ', then in the collector 6, again in the collector 6 ', etc.
[0024] The following temperatures were used: T1> 120 ° C. T2 120 ° C. T3 -25 ° C. 14 -40 ° C. T5 -15 ° C. T6 -90 ° C. T7 -85 ° C. T8 -90 ° C. REFRESHING MODULE FIGURE 2 This module - which is a convenience module - is intended to readjust the pressure of the gaseous effluent leaving the module of FIG. 1 to reach the operating pressure of the operation. treatment. It is not necessarily used if the gaseous effluent to be treated does not contain tars. Since a pressure drop has occurred in the module of Figure 1, it is therefore necessary to restore the pressure of the gaseous effluent. It is the role of this module which includes two air-refrigerators with AR3 and AR4 fogger and a CP1 compressor sandwiched between the two. Line 22 supplies water to the AR4 fogger, a bypass 22a supplying water to the AR3 fogger.
[0025] The gaseous effluent degoudronné coming from the outlet of the pipe 21, at a temperature T4, is discharged to the first aerator-refrigerator AR3, from which it emerges at the lower temperature T9.
[0026] At the outlet of the AR3 aerator, the gaseous effluent has traces of condensed moisture. Moisture is then removed via a purge of water by means of a condensate separator tank BS, which is interposed between the aerator refrigerator AR3 and the compressor CP1. The gaseous effluent is then conveyed to the compressor CP1 by a pipe 24 on which a valve 25 is located, and then leaves the compressor CP1 at the temperature T9 via a pipe 26 on which there is a valve 27 to be forced back towards the aero Refrigerator with misting AR4 from which it emerges by the pipe 28 at temperature T9 and in the compressed state at the relative pressure P of service. As the temperature of the gaseous effluent increased slightly due to the increase in pressure, it was regulated downward by passing the gaseous effluent through the second AR4 aero-refrigerator to return to the T9 value. One or more other stages (CP, AR4) can be provided if the pressure drop correction is judged unsatisfactory. The gaseous effluent at the outlet of the module of FIG. 2 is then directed towards the NMVOC removal module of FIG. 3 or from the drying halogenated elimination module of FIG. 4. In the illustrated example it was operated at a temperature T9 of 15 ° C.
[0027] CONDENSATION VOCULAR ELIMINATING MODULE - Figure 3 This module is based on the principle of the condensation that bubbling in liquid NMVOCs at -10 ° C (T11) comprising the same constituents and proportions of NMVOCs as the gaseous effluent. to be treated makes it possible to separate the NMVOCs by condensation. At -10 ° C, only the NMVOCs are in the liquid state, the rest of the compounds being in the gaseous state. Apparatus The apparatus comprises a column C1, which is a NMVOC removal column, overflow with cooling coil. The filling liquid of the column Cl is a liquid having the same composition or substantially the same composition as the NMVOC composition of the gaseous effluent to be treated. The bottom of the column Cl is equipped with a diffuser whose pores have a diameter of approximately 1 μm, allowing bubbling of the gaseous effluent in the NMVOC treatment liquid at the temperature T11. An "ice-water unit 1" supplies iced glycol water at the temperature T14 at the bottom of the column C1 through the line 29, the water following a serpentine path 30 in the column C1 and emerging in part. higher by the pipe 31 to be returned to the "chiller 1". A bypass 32 of the duct 29 supplies a chilled water exchanger E3, equipped with a condensate trap, to said frozen condensed water, said condensate being evacuated from the latter by a duct 33a on which there is a discharge pump P4 which pump the condensate to discharge it to the "condensate tank 1". The heated fluid exiting the exchanger E3 is sent into line 33b to return to the "ice water group 1". The NMVOCs are withdrawn from the bottom of the overflow column C1 by a pipe 34 by being pumped by a discharge pump P3 into a tank of NMVOCs. A valve 35 is disposed on the pipe 34. The gaseous effluent from the outlet 28 of the module of FIG. 2 at the temperature T9 enters the exchanger E3 and leaves it via the pipe 40 at the temperature T10 to be transferred to the bottom of the column C1. It emerges from the top thereof at the temperature T11, lower than T10, by a duct 41 to be addressed to an inlet of at least one of the modules of FIGS. , 8 or 9. Operation The effluent gas at temperature T9 from the module of FIG. 2 is discharged into exchanger E3 to lower its temperature to T10. As indicated, the exchanger E3 is connected to the chilled water circulation system, fed by the "chilled water unit 1" at temperature 114; and the "chilled water unit 1" also supplies the column Cl. The exchanger E3 is also connected to the evacuation pump P4 which serves to remove the condensate produced during the regulation of the temperature towards the condensate recovery tank. 1 ("condensate tank 1"). The gas cooled at T10 then enters the column at C1 at its lower part.
[0028] The treated gaseous effluent is then bubbled into the column C1. An overflow allows the evacuation of the NMVOC condensed with the aid of the discharge pump P3 to the NMVOC recovery tank. The temperature of the column C1 is maintained at T11 with the aid of the ice water 114 which circulates in the coil 30 inside the column C1. The surplus of NMVOCs eliminated at this stage of the process of the invention It is then burned or sent to the torch and thus constitutes an energy source. In the illustrated example, the following temperatures have been operated: T10 -2 ° C T11 -10 ° C 114-15 ° C 15 ELIMINATION MODULE HALOGEN COMPOUNDS BY SALIFICATION WITH DRYING - FIG. 4 The apparatus comprises a 20 CH overflow column for salification and drying. In the example shown, the column CH is filled with a solution of H2504 (salification and drying liquid). Condensate is withdrawn from the bottom of the CH column by a pipe 36 by being pumped by a discharge pump P6 into a "condensate tank 2". A valve 37 is disposed on the pipe 36. In order to maintain a stable H2504 concentration , a metering pump P5 is used to supply the drying liquid through the line 38 in concentrated H2504 stored in the "H2SO2 tank". A valve 39 is disposed on the pipe 38. At the outlet of Cl, the gaseous effluent of the pipe 41 coming from the module of FIG. 2 or from the module of FIG. 3 is discharged into the column CH filled with the solution of H2SO4 which is designed to remove halogenated compounds and traces of moisture. The overflow allows the evacuation of the condensate and the excess of the H2SO4 solution to the "condensate tank 2" using the pump P6. The concentration of H2SO4 in the liquid of the column CH is regulated using the metering pump P5, while generally being maintained at more than 50% of H2SO4. This step of treatment with H2SO4 makes it possible to eliminate the traces of water present in the gaseous effluent at the temperature T12, as well as the halogenated compounds. T12 is slightly higher than T11 because the gaseous effluent has slightly warmed up. The dry gaseous effluent at temperature T13 is then discharged via line 41a into the desulfurization module of FIG. 5, or into the purification module of FIG. 8 or into the purification module of FIG. The next module depends on the desired treatment yield, which itself depends closely on the quality of the projected treatment, as will be seen below. In the illustrated example, it was operated with a temperature T12 of -8 ° C and a temperature T13 of -7 ° C. 30 DESULFURATION MODULE BY PHYSISORPTION - Figure 5 This module is mainly designed to eliminate H2S. Some compounds such as CO2 and NH3 are automatically or partially eliminated by the physisorption effect. Organic sulphides, such as carbon sulphides, can be deposited and subsequently removed. Apparatus This module comprises two groups of three desulphurization columns each, namely C2, C3 and C4 and C5, C6 and C7, as well as a LP water preparation flask, and a chilled water unit 2. Chilled water at temperature T15 is conveyed via a pipe 42 to a branch 43 which branches into three branches 44 and a branch 45. Each branch 44 gives in a lower branch 46 which feeds, at its two ends, the columns C2 and C5 , C3 and C6, C4 and C7 in ice water. On either side of the point of connection of the branches 44 and 46 there are valves 47. The branch 45 leads to the base of the preparation drum BP. The chilled water at temperature T15 exits from each of the coils of the desulfurization columns C2 to C7 and the flask BP at a temperature T16 into branches 48 (shown with arrows indicating the course of the cooling water) which connect respectively columns C2 and C5, C3 and C6, C4 and C7 each having two valves 49 associated with each of these columns. Between two valves 49 is the point of connection with a branch 50 which is connected to a branch 51, which is connected to a return branch 52 to the chilled water unit 2.
[0029] The outlet 53 of the preparation flask BP is also connected to the branch 51. The flask BP recovers the treated water from the waste water treatment module (FIG. 7) through the outlet 54, which module will be described in greater detail hereinafter. -after. A valve 55 controls the entry of the treated water into the LP column. The pre-cooled water leaving the bottom of the LP column is discharged by the pump P10 through a pipe 56 to be addressed to the upper part of each of the columns C2 to C7, the connection between the columns C2 to C7 and the pipe 56 being ensured by the branches 57 on which are valves 58. The saturated water is withdrawn at the base of each column C2 to C7 by a pipe 59 on which is a valve 60. The pipes 59 are connected to a pipe 61 which directs the saturated water to discharge to the module of Figure 6, reactor 1, which will be described in more detail below.
[0030] The dry gaseous effluent from the outlet 41a of the module of FIG. 4 at the temperature T13 is conveyed by means of a pipe 62 towards the base of the columns C2 and C5, a valve 63 being associated with each of these columns C2 and C5. The gaseous effluent exits at the top in a pipe 64 connected to each of the columns C2 and C5 with a non-return valve 65 associated with each of these columns, and is then sent via a pipe 66 to the pipe 62 connecting the base of the two following columns C3 and C6, and so on until the outlet of the purified gas at the outlet 67 at temperature T17.
[0031] Operation The dry gaseous effluent from the NMVOC elimination module (FIG. 3) or the elimination with drying of the halogenated compounds (FIG. 4) is brought to the temperature T13 to the series of three successive C2, C3 desulfurization columns. and C4. In a first step, the dry gaseous effluent enters the lower part of the desulphurization column C2 in which the temperature is maintained at the temperature T16. The temperature is controlled by means of a "chilled water unit 2" which keeps the water in the system at a temperature T15. The circulation of the frozen glycol water in the coils which are placed inside the desulphurization columns C2 to C7 makes it possible to maintain an appropriate temperature of 2 ° C. preferably, the temperature never exceeding 5 ° C. The dry gaseous effluent is diffused in the first desulfurization column C2 in water at the temperature T16. By a phenomenon of physisorption, 1 L of water can absorb up to 4 L of H2S at a temperature between 2 and 5 ° C. For this reason, the cooling system powered by the "Chilled Water Unit 2" must be precisely and rigorously regulated. Knowing the sulfur composition at the inlet 25 of the desulfurization module installation thanks to the presence of a sulfur detector and the amount of H2S that can be absorbed per volume of water, it is possible to estimate the duration necessary to treat the gaseous effluent according to the volume of water contained in each desulfurization column. When the sulfur detector at the outlet of the last desulphurization column at line 67 indicates the presence of sulfur in the gaseous effluent leaving the series of desulfurization columns, this indicates that the desulfurization columns C2, C3 and C4 are saturated. Then, the dry gaseous effluent is sent to the second series of three desulfurization columns C5, C6 and C7. The supply lines 62 leading to the inlet of the desulfurization columns C2 to C7 are provided with valves 63 which make it possible to direct the entry of dry gaseous effluent into the appropriate circuit. At the same time, a desulphurization solution circuit, which consists essentially of water, makes it possible to feed the desulfurization columns C2 to C7 and to renew their contents each time the desulfurization solution arrives at saturation. A preparation flask BP containing the desulfurization solution is maintained at the temperature T16. The water is conveyed by means of the pump P10 to the desulphurization columns C2 to C7 at their upper part and is directed at the outlet towards the water treatment module of FIG. 6 - reactor 1 by the pipe 61 which leaves from their lower part. The filling of the desulfurization columns C2, C3 and C4 is alternating with that of the desulfurization columns C5, C6 and C7. The removal of the sulfur compounds at the first C2 (or C5) desulfurization column is generally 36-38% by volume, it is generally 32-35% by volume at the second C3 desulfurization column (or C6) then generally 30-32% by volume at the third column C4 (or C7). This module can be adopted for the removal of H2S with 4 NL of H2S / 1 1 of water. Incidentally, it can be stated that, in the same way, this module can be adopted to remove NH3 at the rate of 1000 NL of NH3 / 1 1 of water, SO2 with 63 NL of SO 2/1 1 of water and CO2 at a rate of 1.4 NL CO2 / 1 L of water provided that the temperature of the process water is maintained at 2-5 ° C. In fact, if it is desired to remove H2S, at the same time at least partially NH3 and CO2 will be removed. Returning to the removal of H2S, in the desulfurization columns, the water saturated with pollutants separated from the gaseous effluent will in turn be sent to the module of Figure 6 (Reactor 1). In the illustrated example, the following temperatures were used: T15 -5 ° C. T16 2 ° C. T13 -7 ° C. T17 -4 ° C. LIQUID-GAS SEPARATION MODULE - FIG. 6 (Reactor 1) AND DETAILED DESCRIPTION VALUATION OF H2S (WITH CO2) BY CHEMICAL ABSORPTION OF H2S IN H2SO4 - FIG. 6 (Reactor 2) Apparatus 20 It comprises a degassing reactor 1 which is supplied at the top by the outlet 61 of the desulfurization module of FIG. method of saturated gaseous pollutants) and from which leads a conduit 68 of the charged water to the inlet of the water treatment module 25 of Figure 7 which will be described in more detail below. The reactor 1 is equipped with a mechanical stirrer with motor 69 whose mission is the physical separation between the two aqueous and gaseous phases of the saturated desulfurization water.
[0032] The gaseous phase withdrawn at the top of the reactor 1 will be conveyed by means of a blower S2 through the pipe 70 to the reactor 2.
[0033] Operation The water mainly saturated with H2S and CO2 from the desulfurization module of Figure 5 is first degassed inside the reactor 1. The engine 69 generates turbulence inside the reactor 1, leading to the separation between the aqueous phase and the gas phase of the desulfurization water. The aqueous phase is directly discharged from the lower part of the reactor 1 towards the water treatment module of FIG. 7 via line 68. The gas phase is discharged to reactor 2 which contains acetic acid. where it is converted to H2SO4 according to the following reaction: CH3COOH +2 CO2 + H2S H2SO4 +4 C +2 H2O H2SO4 + water are sent to a storage tank. Carbon, a by-product of the reaction, is sent to a reaction by-product storage tank. The fraction of unreacted CO2 is removed in the vent which is released into the atmosphere. CHARGED WATER TREATMENT MODULE - FIG. 7 Apparatus It consists of two parallel-connected Fia, Fib substrate filters (such as activated carbon) fed from the module of FIG. Reactor 1. The output 71 of the Fia, Fib substrate filters is sent to three ordinary prefilters special reverse osmosis F2, F3, F4 in series, then through a high pressure pump P7, a water osmosis of which the outlet 54 is addressed to the LP preparation tank of the desulfurization module of Figure 5, and the outlet 72 is addressed to a retentate recovery.
[0034] A non-return valve 73 is arranged on the outlet of the ordinary prefilter special water-softener F4 and a valve 74, at the entrance of the ordinary pre-filter special osmosis F2. A makeup of water arrives through the pipe 75 in the pipe 71, a valve 76 being disposed on this pipe 75. Operation Polluted water, mainly loaded with organic sulphides, at the outlet of the module of Figure 6 - Reactor 1 enters the upper part of a Fia or Fib substrate filter. One of the filters replaces the other when the first one reaches saturation. An output detector makes it possible to determine whether the filtration is still effective or whether it is necessary to direct the polluted water towards the second filter. The organic sulfides and mercaptans, sulfur compounds in the solid state not removed during the previous step which eliminates only the sulfur in the gaseous state in the form of H 2 S, are in particular captured by these Fia substrate filters or Fib. The water exits the bottom of the filters to be directed to three standard prefilters F2, F3 and F4 connected in series and then to a reverse osmosis membrane osmosis unit to return to the preparation tank BP of the desulphurization module of the reactor. Figure 5. The expected water make-up makes it possible to bring the necessary adjustment in water following the losses generally of 5 to 10% by weight of the overall water during (filtration and) stirring at room temperature. previous step, during the liquid-gas separation of Figure 6 - Reactor 1. This module of Figure 7 allows (the preparation and) regeneration of process water. This equipment comprises three overflow columns C8, C9 and C10, a storage tank connected to a metering pump P9 and a recovery tank connected to an evacuation pump P8. The gaseous effluent is fed through line 41a into the lower part of the overflow column C8 where it will bubble. It emerges at the top through the pipe 84 to enter the lower part of the overflow column C9 from which it emerges at the top through the pipe 85 to enter the lower part of the overflow column C10. A storage tank is connected to a metering pump P9 via line 86 which branches into three lines 87a, 87b and 87c provided with valves 88a, 88b and 88c, respectively, to supply columns C8 to C10, respectively. . A collection tank will recover the reaction product through a discharge pump P8 which allows the collection of the product from columns C8 to C10 through lines 89a, 89b and 89c, respectively, which are provided with valves 90a, 90b and 90c, respectively. Operation The dry gaseous effluent from the module of Figure 2 or the NMVOC processing module of Figure 3 or from the processing module of the halogenated compounds with drying of the gas of Figure 4 is discharged at the bottom of the column. C8 filled with CH3COOH which comes from the storage tank. The following reaction takes place, the reaction being similar to that taking place in reactor 2 of the module of FIG. 6: H 2 S + 2 CO 2 + CH 3 COOH H 2 SO 4 + 4 C + 2 H 2 O In this case, the overflow columns are filled with CH3COOH from the "storage tank" and carbon and sulfuric acid are recovered in the "recovery tank". It is also possible to aim for the elimination of NOMs, such as NO2 + NO, according to the following reaction: NO2 + NO + 2 H2O2 2 HNO3 + H2O In this case, the overflow columns are filled with H2O2 from the " storage tank "and the HNO3 solution is recovered in the" recovery tank ". The same reaction takes place in each of the overflow columns C8, C9 and C10, in which the proportion of pollutant decreases progressively with respect to the previous column.
[0035] The elimination of the pollutant targeted by the treatment in the first column C8 is generally 36-38% by volume, it is generally 32-36% by volume at the level of the second column C9 and then 30-32% by volume. volume at the third column level C10. The choice of the method to be used depends on the composition of the gas to be treated. If there is a small concentration of pollutant (CO2 and H2S), it is not necessarily necessary to go through the modules of Figures 5, 6 and 7, but it is better to go directly to the treatment by This intermediate module of FIG. 8 was operated with a temperature T11 of -10 ° C. and a temperature T13 of + 7 ° C.
[0036] FIGURE 9 Apparatus It consists of: - a CdP sputtering plant comprising a compressor CP2, two columns 77a / 77b and a reagent storage tank, a reactor 78 in which there is, in part high, a ramp 79 spraying the reagent and, in the lower part, a ramp 80 of water spray arriving through the pipe 81; and a screw pump PaV, the inlet 82 of which is connected to the base of the reactor 78 and to the outlet 83 from which the reaction product leaves. Operation The dry gaseous effluent from the module of FIG. 2 or FIG. treatment of the NMVOCs of FIG. 3 or the treatment module of the halogenated compounds with drying of FIG. 4 is brought by the pipe 41a to the lower part of the reactor 78. A bubbling system by means of a diffuser is present in the part lower reactor 78.
[0037] The dry gaseous effluent can be if necessary (see reactions below) first humidified as illustrated in Figure 9 (or receive a solution of hydrogen peroxide instead of the humidification water) by means of the vaporization of water via the ramp 80 of water spray arriving via line 81. At this level takes place a chemical modification of some polluting compounds: CO2 in the presence of water will give H2CO3 and SO2 in the presence of water will generate H2S03. The humidified gaseous effluent is then exposed to the reagent which is sprayed through the reagent spray boom 79. The reagent is stored in a storage tank at the CoP spraying plant. This reagent is formulated according to the pollutant to be eliminated.
[0038] The powder form reagent will be pressurized in columns 77a and 77b to facilitate spraying. The resulting product is sprayed at the reagent spray boom 79. In reactor 78, the following reactions can take place: (1) To eliminate H2S, two treatment reagent formulations are possible: - Cu (OH) 2 + H2S if> CuS + 2H 2 O (this type of reagent will be used in the case where the gaseous effluent to be treated does not contain CO2); or - if the gaseous effluent contains CO2, the reagent Ca (OH) 2 is used. The treatment will be established according to the following reaction: H 2 S + Ca (OH) 2 + 2 CO 2> CaSO 4 + 2 C + 2 H 2 O (a CaO type catalyst may be added to the reagent composition). (2) To remove CO2, the reagent Ca (OH) 2 is used. The reaction proceeds as follows: CO2 + H2O if> H2CO3; H2CO3 + Ca (OH) 2 if> CaCO3 + 2 H2O (3) To eliminate SO2, the treatment is established according to the following reactions: SO2 + H2O if> H2S03 2 H2S03 + 2 Ca (OH) 2 + CO2 if> 2 CaSO4 + C + 4 H2O (in the presence of CO2) H2S03 + Ca (OH) 2 if> CaSO3 + 2 H2O (in the absence of CO2) The reaction can always be pushed or catalyzed by CaO, another reagent or by readjustment pH. (4) To eliminate the NOMs, the reagents H2O2 and Ca (OH) 2 are used. The reaction proceeds as follows: NO2 + NO + 2 H2O2 if> 2 HNO3 + H2O2 HNO3 + Ca (OH) 2 if> Ca (NO3) 2 + 2 H2O The addition of H202 is at the same level as that of the water spray (humidification of the gaseous effluent).
[0039] The reaction product will be removed at the bottom of reactor 78 and pass through a PaV screw pump. It is also possible to carry out the reactions separately, in a staged manner, and initially eliminate only H2S, then CO2, etc. . This depends on the reaction product that we want to recover and value. The installation and choice of reagent will depend on the user's request and the composition of the raw gaseous effluent. The treated gaseous effluent will be recovered at the upper part of the reactor 78. The quality of the treated gaseous effluent depends closely on the efficiency of the reaction carried out. It should be noted that the reactions mentioned in (1) to (4) can be carried out by means of spraying techniques (pressurized liquid), misting (liquid / gas [air] mixture under pressure) or bubbling (gaseous dispersion in an absorption liquid). FIG. 10 represents a flowchart which makes it easier to visualize the sequence of the processing modules according to the needs of the user. The choice of the method and more particularly of the desulphurization module to be used among the module of FIG. 5, the purification module of FIG. 8 and the purification module of FIG. 9 is carried out according to: the concentration pollutants contained in the gaseous effluent to be treated, the flow rate of the raw gas to be treated and the desired quality of the purified gaseous effluent.
[0040] The entirety of the polluting compounds (mainly H2S and NMVOC) can be eliminated by the process of the invention. If one considers the synthesis gas, including the tar concentration, the process of the invention also makes it possible to eliminate these tars via the module of FIG. 1.

权利要求:
Claims (13)
[0001]
CLAIMS1 - Process for the purification of a gaseous effluent containing pollutants chosen from tars, non-methane volatile organic compounds (NMVOCs), halogenated compounds, hydrogen sulfide (H2S), ammonia (NH3), sulfur dioxide (SO2), nitrogen oxides (N0x) and carbon dioxide (CO2), characterized in that the gaseous effluent to be purified is analyzed to identify the pollutants that it contains, and then that the following successive operations are carried out according to the identified pollutants: (1) at least partial, advantageously complete, elimination of the tars by cooling the raw gaseous effluent to pass the tars from their gaseous state to their liquid state and physically separating them to recover a treated gaseous effluent; (2) at least partial, advantageously complete, removal of the NMVOCs by bubbling the gaseous effluent into a liquid mixture of NMVOCs of the same composition as that of the NMVOCs present in the gaseous effluent to be treated in order for the gaseous NMVOCs to condense and joining said liquid mixture, and recovering the treated gaseous effluent; (3) at least partial, advantageously complete, elimination of the halogenated compounds by bubbling the gaseous effluent into a salification solution, the salification allowing simultaneous drying of the gaseous effluent, and recovery of the treated gaseous effluent; (4) at least partial removal of at least one of H2S, NH3, SO2, CO2 and NOx by selecting from: (4a) at least partial removal of at least one of H2S, NH3, SO2 and CO2 by passing the gaseous effluent through chilled water in which said gaseous H 2 S, NH 3, SO 2 and CO2 are trapped in this state by physisorption, the process water which is saturated with said gaseous pollutants being separated to obtain a gaseous effluent treated; or (4b) at least partial removal of H2S in the case where CO2 is co-present with it, by bubbling the gaseous effluent into a liquid allowing the chemical absorption of H2S with simultaneous removal of at least a part of the CO2, or at least partial NOx removal by bubbling the gaseous effluent into a liquid for chemical absorption thereof, and recovering the treated chemical effluent; or (4c) elimination in any order of: - H2S alone or with CO2 by spraying in a stream of the gaseous effluent of a reagent able to combine with respectively H 2 S or H 2 S + CO2 to give a reaction product solid which is removed from the gaseous effluent to recover it in the purified state; - SO2 alone or CO2 alone or SO2 + CO2 by humidification of the gaseous effluent, then spraying in the humidified gaseous effluent of a reagent capable of combining with the reaction product between the humidifying water and respectively SO2 or CO2 or SO2 + CO2 to give a final reaction product that is removed from the gaseous effluent to recover it in the purified state; and- NOx alone by reaction of the gaseous effluent with H 2 O 2 and then spraying in the gaseous effluent thus treated with a reagent capable of combining with the reaction product between H 2 O 2 and NOx to give a final reaction product which the gaseous effluent is removed to recover it in the purified state.
[0002]
2 - Process according to claim 1, characterized in that the gas to be treated is selected from natural gas, gas associated with the extraction of petroleum, biogas, synthesis gas and industrial gaseous discharge.
[0003]
3 - Process according to one of claims 1 and 2, characterized in that in (1), is passed the gaseous effluent to be degoudronner in at least one vertical tube heat exchanger connected to its base , at a tars collector, said gaseous effluent passing outside the tubules and a cooling fluid passing inside the tubules, the tars liquefying along the tubules to flow gravitarily and be collected in the collector.
[0004]
4 - Process according to claim 3, characterized in that one uses two heat exchangers tube bundle (E2, E2 '), connected, at their base, to a tars collector and a third heat exchanger (El ) of the same type but without a tars collector and the gaseous effluent is passed through the following two successive sequences: in the first sequence, the gaseous effluent is passed at a temperature T1 greater than 120 ° C. in a first exchanger with collector (E2 ') without subjecting it to heat exchange, then in the exchanger without collector (El) where it undergoes heat exchange to cool it to the temperature T2 of 120 ° C + 2 ° C, then in the other exchanger with collector (E2) for cooling to a temperature T3 of 25 ° C, the tars being retained in the walls of said exchanger (E2) outside its tubules, the tapped gas exiting said exchanger E2 '; and in the second sequence, the gaseous effluent which continues to arrive at the temperature T1 is no longer passed in the exchanger E2 'but in the exchanger E2 without subjecting it to heat exchange, causing the fluidification of the tars. retained in it, which then flow and can be collected in the associated collector (6), then in the collectorless heat exchanger (El) where it undergoes heat exchange to cool it to a temperature T2 of 120 ° C + 2 ° C, then in the other heat exchanger with collector (E2 ') to cool it to a temperature T3 of 25 ° C, the tars being retained in the walls of said exchanger E2' outside its tubules, the tapped gas leaving said exchanger E2 '; then the cycle E2'-E1-E2 and E2-E1-E2 is repeated as soon as it arrives from the gaseous effluent.
[0005]
5 - Process according to one of claims 1 to 4, characterized in that in (2), is passed the gaseous effluent to be treated in an overflow column (C1) with cooling coil, containing said mixture liquid, maintained at a temperature of -10 ° C + 2 ° C, the bubbling in said Cl column to eliminate the NMVOC gaseous effluent to be treated by the phenomenon of condensation.
[0006]
6 - Process according to one of claims 1 to 5, characterized in that in (3), the gaseous effluent to be treated is bubbled in an overflow column (CH) filled with an acid solution sulfuric solution as a salting solution, the bubbling in said solution for removing the halogenated compounds present in said gaseous effluent at the same time as traces of water if they exist.
[0007]
7 - Process according to one of claims 1 to 6, characterized in that in (4a), the separated process water, saturated with said gaseous pollutants and which may also contain pollutants in the solid state is addressed to a separation reactor, on the one hand water charged with any solid pollutants and, on the other hand, gas, the water, if it is loaded with solid pollutants, then being filtered to eliminate these pollutants and advantageously recycled to the stage (4a).
[0008]
8 - Method according to one of claims 1 to 6, characterized in that in (4a), for the removal of H2 S, is passed the gaseous effluent to be treated in desulfurization columns (C2 to C7) filled with chilled water at a temperature between 2 ° C and 5 ° C, constituting a desulphurization stage, said water, by an H2S absorbing physisorption phenomenon at a ratio of 1 L of water per 4 L of H2S, the process water loaded with gaseous pollutants and possibly with solid organic sulphides being sent to a water / gas separation reactor, and the water separated during this degassing, if it is loaded with organic sulphides, being treated with filtration and reinjected as treated water in the desulfurization stage, the desulfurization columns being advantageously arranged in two series connected in parallel, each series comprising three columns connected in series, the columns of the two series (C2-C3-C4) being in turn desulphurization service and regeneration service of the process water.
[0009]
9 - Process according to claim 8, characterized in that the gas separated at the liquid / gas separation reactor containing H2S and CO2 is sent to a reactor containing an acid solution, such as acetic acid, for converting the H2S and at least a portion of the CO2 present in the gas, the carbon and the sulfuric acid solution obtained being sent to storage tanks and the possible fraction of unreacted CO2 being rejected in the atmosphere.
[0010]
10 - Process according to one of claims 7 to 9, characterized in that in the filtration step, the separated liquid is passed through one or more filters (Fia, Fib) substrate such as activated carbon, the various filters being advantageously mounted in parallel for alternating operation in the case where one is saturated, for capturing pollutants in the solid state, then in at least one filter F2, F3, F4 in series to remove impurities remaining fines, and then in a water osmosis unit to obtain a quality water advantageously reinjected to the desulphurization stage.
[0011]
11 - Method according to one of claims 1 10, characterized in that in (4b), the effluent to be purified is bubbled in a series of columns overflow at room temperature, the overflow columns (C8, C9 and C10 ) containing a solution of acid, such as acetic acid, for conversion of the H2S and CO2 present in the gas, the carbon and the sulfuric acid solution obtained being sent to recovery tanks, and the gaseous effluent at least partially desulfurized being recovered at the outlet of the last column.
[0012]
12 - Process according to one of claims 1 10, characterized in that in (4b), the effluent to be purified is bubbled through a series of overflow columns at room temperature, the overflow columns (C8, C9 and C10) containing a solution of oxygenated water for conversion of NOx present in the gas, the obtained HNO3 being sent to a recovery tank, and the gaseous effluent at least partially free of NOx being recovered at the outlet of the last column .
[0013]
13 - Method according to one of claims 1 12, characterized in that in (4c), diffuses the gaseous effluent in an updraft in a reactor having, in its lower part, a device, such as a ramp, water supply or H202 solution when humidification or reaction with H202 respectively is provided, in its upper part, a device, such as a ramp, reagent spray, and, in the lower part a device for recovering the end products of reaction, the reagents applied being in particular Cu (OH) 2 in the case of the elimination of H2S alone; Ca (OH) 2 in the case of the removal of H2S + CO2; of Ca (OH) 2 in the case of removal of CO2 alone H2CO3 reaction resulting from the reaction CO2 + H2O with Ca (OH) 2; of Ca (OH) 2 in the case of removal of SO2 alone or SO2 + CO2 by humidification followed by treatment with Ca (OH) 2; of Ca (OH) 2 in the case of removal of NOx alone by reaction with H 2 O 2 and then by chemical absorption of HNO 3 on Ca (OH) 2 O 10

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同族专利:

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CN112410078A|2020-11-04|2021-02-26|山东义丰环保机械股份有限公司|A sweetener for coal gas|

法律状态:
2016-01-20| PLFP| Fee payment|Year of fee payment: 3 |

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2017-03-24| PLFP| Fee payment|Year of fee payment: 4 |

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2018-03-09| PLFP| Fee payment|Year of fee payment: 5 |

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2019-11-29| ST| Notification of lapse|Effective date: 20191106 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1452024A|FR3018461B1|2014-03-11|2014-03-11|PROCESS FOR THE CLEANING OF GASEOUS EFFLUENTS BY SELECTIVE REMOVAL OF THE POLLUTANTS CONTAINED THEREBY|FR1452024A| FR3018461B1|2014-03-11|2014-03-11|PROCESS FOR THE CLEANING OF GASEOUS EFFLUENTS BY SELECTIVE REMOVAL OF THE POLLUTANTS CONTAINED THEREBY|

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EP15158576.7A| EP2918327B1|2014-03-11|2015-03-11|Method for purifying gaseous effluents by selective removal of the pollutants contained therein|