EP1480908A1 - Method for drying of hydrogen chloride from aqueous hydrogen chloride solutions - Google Patents

Method for drying of hydrogen chloride from aqueous hydrogen chloride solutions

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Publication number
EP1480908A1
EP1480908A1 EP03717366A EP03717366A EP1480908A1 EP 1480908 A1 EP1480908 A1 EP 1480908A1 EP 03717366 A EP03717366 A EP 03717366A EP 03717366 A EP03717366 A EP 03717366A EP 1480908 A1 EP1480908 A1 EP 1480908A1
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EP
European Patent Office
Prior art keywords
hydrogen chloride
drying
anhydrous
cacl
hci
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.)
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Application number
EP03717366A
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German (de)
French (fr)
Inventor
Régis Loze
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.)
Kem One SAS
Original Assignee
Atofina SA
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Filing date
Publication date
Application filed by Atofina SA filed Critical Atofina SA
Publication of EP1480908A1 publication Critical patent/EP1480908A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • B01D53/26—Drying gases or vapours
    • B01D53/261—Drying gases or vapours by adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/07—Purification ; Separation
    • C01B7/0706—Purification ; Separation of hydrogen chloride
    • C01B7/0718—Purification ; Separation of hydrogen chloride by adsorption

Definitions

  • the present invention relates to a method for drying hydrogen chloride (HCl gas) from aqueous hydrochloric solutions (of different concentrations) obtained in particular during the recovery of chlorinated residues (HRV).
  • HCl gas hydrogen chloride
  • HRV chlorinated residues
  • chlorinated organic compounds generates abundant quantities of by-products and residues often containing chlorine.
  • residues can be present either in the form of a gas, for example in the case of the manufacture of vinyl chloride, or of its polymers or copolymers, or in the form of liquid and / or of tarry solids obtained in the manufacture.
  • aliphatic, cycloaliphatic, and / or aromatic chlorinated hydrocarbons aliphatic, cycloaliphatic, and / or aromatic chlorinated hydrocarbons.
  • the composition of these chlorinated residues varies according to their origin. Certain residues include chlorinated tar products, at least some of the constituents of which contain more than 7 carbon atoms per molecule.
  • Other chlorinated residues include chlorinated C compounds and / or chlorinated C 6 compounds.
  • chlorinated residues can be accompanied by other compounds comprising chlorinated C1 to C constituents.
  • chlorinated residues may also include polychlorinated biphenyls (PCBs) used as dielectric and cooling fluids and which one wishes to get rid of given the ban on the use of these products.
  • PCBs polychlorinated biphenyls
  • the burning of these chlorinated liquid and / or gaseous residues is carried out by the applicant in the presence of an excess of air and water at temperatures ranging from 900 ° C to 1450 ° C, and generally, included between 1,200 ° C and 1,300 ° C in an installation comprising in particular a burner into which chlorine residues are injected and an oxidizer; said burner being in connection with an oven.
  • the hot gases leaving the furnace leave part of their sensible heat in a boiler supplying steam and are then suddenly cooled in a quenching reactor.
  • the hydrogen chloride formed is absorbed in absorbers, which leads to aqueous solutions commercial hydrochloric acid concentrates at around 30% by weight of HCl. Any chlorine formed is absorbed in an alkaline aqueous solution.
  • aqueous hydrochloric solutions can be sold as is for applications such as neutralization of alkaline effluents, preparations of metal chlorides, attack of metals, or can be treated to lead to more or less anhydrous hydrogen chloride.
  • HCI gas can be used in particular for the manufacture of vinyl chloride obtained by thermal cracking of 1,2-dichloroethane, which is synthesized in particular by oxychlorination of ethylene, depending on the reaction:
  • the operation is carried out according to the process described below, shown diagrammatically in FIG. 1.
  • the 30% hydrochloric aqueous solution coming from absorbers of an HRV unit is directed to a concentration column (1) then then to a distillation column ( 2).
  • the HCl gas obtained in (9) contains approximately 50 to 150 pp of water.
  • the Applicant has found that the use of such a gas for the oxychlorination of ethylene leads to significant corrosion problems of the compressors used to bring HCl gas to a (operating) pressure of approximately 6 to 7 bars. These compressor corrosions lead to lower compression ratios leading to frequent shutdowns for reconditioning. This results in high and costly maintenance.
  • This water content in HCI gas can be easily measured by determining the dew point (or starting liquefaction temperature of acidic water) by lowering the temperature of a sample of HCI gas at a given pressure.
  • FIG. 2 schematically represents the drying method described in WO 0112541 using H 2 5O 4 which makes it possible to perfect the drying of an HCl gas and to bring its water content less than 0.5 ppm or even less than 0.15 ppm.
  • the HCl gas to be treated arrives at (81) in a packed column (92).
  • the dry H 2 SO is taken from a storage (82) and then brought to a ventilated tank (84).
  • H 2 5O 4 sec (86) is pumped to a liquid ring compressor (88) or it is brought into contact with HCl partially dry gas (90) coming from the head of a first packed absorption column ( 92), which receives HCI gas to be dried (81) and with a stream (94) d ⁇ 2 SO partially wet recycled from a second packed absorption column (96).
  • the partially dried HCI (90) from (92) is then dried in (96) to provide anhydrous HCI (98).
  • the partially wet H 2 S0 4 at the bottom of (96) partially recycled to said column feeds the compressor (88) via (100) and the column (92) via (102) where it is brought into contact against the current. with the HCl gas stream to be dried (81).
  • the wet H 2 50 4 obtained at the bottom of (92) is recycled partly at the top of said column (92) and partly in a stripping column (106) which uses dry air (108) to remove HCI residual wet H 2 SO, which HCI is eliminated at the top (110).
  • the wet H 2 SO, free of HCI, is recovered in a storage tank (114) where it is subsequently dried for reuse.
  • anhydrous HCl gas can be obtained more simply, obtained during the distillation of aqueous hydrochloric solutions originating in particular from HRV, by avoiding the drawbacks mentioned previously by using, under certain conditions, anhydrous CaCl 2 .
  • the subject of the invention is therefore a process for drying hydrogen chloride originating from the distillation of aqueous hydrochloric solutions obtained in particular during the recovery of chlorinated residues, characterized in that said hydrogen chloride is brought into contact with chloride anhydrous calcium (CaC ⁇ z) for a period of time less than or equal to 1 minute and, preferably, between 5 seconds and 45 seconds.
  • chloride anhydrous calcium CaC ⁇ z
  • the HCI gas comes from a chlorinated residue recovery plant (HRV) as described above and has a water content generally between 150 and 200 ppm.
  • the anhydrous CaCl 2 which can be used according to the present invention is found to be in the form of beads with a diameter less than or equal to 5 mm and, preferably, with a diameter ranging from 1 to 5 mm.
  • the drying of the hydrogen chloride is carried out at a temperature ranging from -30 ° C to 20 ° C and, preferably, ranging from -15 ° C to -10 ° C. It is generally carried out at a pressure equal to or greater than atmospheric pressure, and preferably at the distillation pressure supplying the HCl humid gas to be dried.
  • the residence time or contact time of the gas HCI with the CaCI 2 anhydrous must be sufficient to absorb the residual water. It depends on the load used and the flow rate of humid HCI gas to be dried.
  • this time is equal to or less than 1 min, generally, this residence time ranges from 5 sec to 45 sec.
  • this residence time ranges from 5 sec to 45 sec.
  • the lifetime of the anhydrous CaCI 2 used can be calculated by taking into account the mass of water absorbed per mass of anhydrous CaCI 2 used.
  • the Applicant has found that it is necessary to change the load of CaCI 2 when the latter has increased by 30% by weight at most and, preferably, when the load has increased by 25 to 30%.
  • the water content in the HCl gas having passed through the CaCI 2 feed can be easily obtained by determining the dew point of the outgoing HCl gas.
  • the method according to the present invention can be implemented by means of a device as shown diagrammatically in FIG. 3.
  • a vertical cylindrical column (01) comprising at least one basket (02) containing the charge of anhydrous CaCl 2 , having at its base a bottom grid (03) provided with interlaced strips and a support grid (04) on which a canvas (05); at the upper part of said basket also rests on the load of CaCl 2 a fabric (06);
  • a cylindrical bottom (07) provided with an HCI gas inlet (08) in junction with an injection “saber” (09) provided with staggered holes (not shown in FIG. 3), and a purge (10); - a cylindrical cap (11) provided with a dry HCI outlet (12) and lifting lugs (13).
  • the fabrics (04) and (05) are made of a material resistant to HCl and have meshes of diameter equal to approximately 1 mm.
  • the charge of CaC ⁇ z is easily replaced due to the simplicity of the device used.
  • This replacement consists of removing the cap (11), removing the basket containing the used charge and replacing a new basket containing a new charge of CaCI 2 .
  • the cylindrical column (01), the bottom (06), the cap (10), as well as the injection saber (08) and the grids (03) and (04) are made of corrosion resistant materials such as ebonity steel. , polypropylene wrapped in a composite material.
  • the basket (s) is (are) made of high density polypropylene
  • the process according to the invention has great flexibility, has the advantage of using a simple and inexpensive device which can be easily inserted into existing units and results in an HCl gas having water contents of less than 20 ppm or even less than 10 ppm.
  • the bottom grids (03) have an outside diameter of 0.905 m and the support grids (04) have an outside diameter of 0.91 m;
  • the fabrics (04) and (05) have meshes of diameter equal to 1 mm and are made of PPHD.
  • the column is made of high density polypropylene, wrapped in a polyester glass laminate.
  • Each basket is loaded with 1.3 tonnes of anhydrous CaC ⁇ z which is in the form of beads from 1 to 5 mm in diameter.
  • the HCl gas to be dried comes from the distillation of hydrochloric solutions from an HRV unit as described above and shown diagrammatically in Figure 1 (outlet (7)).
  • This HCl gas has an average water content equal to 200 ppm and is introduced in (08) at a flow rate varying between 0.5 and 2.5 t / h at a temperature of -13 ° C.
  • the pressure in the device is 0.8 bar relative.
  • the water content in HCI leaving at (12) is determined periodically by the dew point method and a dew point of -24 ° C. is found (measured at atmospheric pressure), which corresponds to a water content about 15 ppm.

Abstract

The invention relates to a method for drying hydrogen chloride from hydrochloric aqueous solutions, according to which said hydrogen chloride is reacted with anhydrous CaCl2 in certain conditions. The inventive method is particularly suitable for hydrogen chloride produced by distilling hydrochloric aqueous solutions that have been obtained during recycling of the chlorinated residues (VRC).

Description

03 00307 03 00307
11
Procédé de séchage de chlorure d' hydrogène provenant de solutions aqueuses chlorhydriques.Process for drying hydrogen chloride from aqueous hydrochloric solutions.
La présente invention concerne un procédé de séchage du chlorure d'hydrogène (HCI gaz) provenant de solutions aqueuses chlorhydriques (de différentes concentrations) obtenues notamment lors de la valorisation des résidus chlorés (VRC).The present invention relates to a method for drying hydrogen chloride (HCl gas) from aqueous hydrochloric solutions (of different concentrations) obtained in particular during the recovery of chlorinated residues (HRV).
La fabrication industrielle de composés organiques chlorés engendre d'abondantes quantités de sous-produits et de résidus contenant souvent du chlore. Ces résidus peuvent se présenter soit à l'état de gaz comme par exemple dans le cas de la fabrication du chlorure de vinyle, ou de ses polymères ou copolymères, soit à l'état de liquide et /ou de solides goudronneux obtenus dans la fabrication d'hydrocarbures chlorés aliphatiques, cycloaliphatiques, et /ou aromatiques. La composition de ces résidus chlorés varie suivant leur origine. Certains résidus comprennent des produits goudronneux chlorés dont au moins quelques uns des constituants renferment plus de 7 atomes de carbone par molécule. D'autres résidus chlorés comprennent des composés en C chlorés et/ou des composés en C6 chlorés. Ces résidus chlorés peuvent être accompagnés d'autres composés comprenant des constituants en Ci à C chlorés. Ces résidus chlorés peuvent également comprendre des polychlorobiphenyles (PCB) utilisés comme fluides diélectriques et de refroidissement et dont on souhaite se débarrasser compte tenu de l' interdiction de l'utilisation de ces produits.The industrial manufacture of chlorinated organic compounds generates abundant quantities of by-products and residues often containing chlorine. These residues can be present either in the form of a gas, for example in the case of the manufacture of vinyl chloride, or of its polymers or copolymers, or in the form of liquid and / or of tarry solids obtained in the manufacture. aliphatic, cycloaliphatic, and / or aromatic chlorinated hydrocarbons. The composition of these chlorinated residues varies according to their origin. Certain residues include chlorinated tar products, at least some of the constituents of which contain more than 7 carbon atoms per molecule. Other chlorinated residues include chlorinated C compounds and / or chlorinated C 6 compounds. These chlorinated residues can be accompanied by other compounds comprising chlorinated C1 to C constituents. These chlorinated residues may also include polychlorinated biphenyls (PCBs) used as dielectric and cooling fluids and which one wishes to get rid of given the ban on the use of these products.
Un moyen de résoudre le problème de l'accumulation de ces résidus et de la pollution de l'air et/ou des eaux dans lesquelles ils peuvent être déversés est de les brûler à haute température, dans une chambre de combustion avec récupération d'acide chlorhydrique gazeux que l'on peut valoriser sous forme de solutions aqueuses, et éventuellement co-production de vapeur d'eau.One way to solve the problem of the accumulation of these residues and the pollution of the air and / or the waters into which they can be discharged is to burn them at high temperature, in a combustion chamber with acid recovery gaseous hydrochloric acid which can be recovered in the form of aqueous solutions, and possibly co-production of water vapor.
Plus précisément, le brûlage de ces résidus liquides et/ou gazeux chlorés est réalisé par la demanderesse en présence d'un excès d'air et d'eau à des températures allant de 900°C à 1 450°C, et généralement, comprises entre 1 200°C et 1 300°C dans une installation comprenant notamment un brûleur dans lequel sont injectés les résidus chlorés et un comburant ; ledit brûleur étant en liaison avec un four. Les gaz chauds sortant du four abandonnent une partie de leur chaleur sensible dans une chaudière fournissant de la vapeur et sont ensuite refroidis brutalement dans un réacteur de trempe. Le chlorure d'hydrogène formé est absorbé dans des absorbeurs, ce qui conduit à des solutions aqueuses chlorhydriques commerciales concentrées à environ 30 % en poids d'HCI. Le chlore éventuellement formé est absorbé dans une solution aqueuse alcaline. Les fumées rejetées dans l'atmosphère ne contiennent plus que de très faibles teneurs en chlore libre et autres polluants. Les solutions aqueuses chlorhydriques à 30 % peuvent être commercialisées en l'état pour des applications telles que neutralisations d'effluents alcalins, préparations de chlorures métalliques, attaque des métaux, ou peuvent être traitées pour conduire à du chlorure d'hydrogène plus ou moins anhydre (HCI gaz). L'HCI gaz peut être utilisable notamment pour la fabrication du chlorure de vinyle obtenu par crackage thermique du 1,2-dichloroéthane, lequel est synthétisé notamment par oxychloration de l'éthylène, selon la réaction :More specifically, the burning of these chlorinated liquid and / or gaseous residues is carried out by the applicant in the presence of an excess of air and water at temperatures ranging from 900 ° C to 1450 ° C, and generally, included between 1,200 ° C and 1,300 ° C in an installation comprising in particular a burner into which chlorine residues are injected and an oxidizer; said burner being in connection with an oven. The hot gases leaving the furnace leave part of their sensible heat in a boiler supplying steam and are then suddenly cooled in a quenching reactor. The hydrogen chloride formed is absorbed in absorbers, which leads to aqueous solutions commercial hydrochloric acid concentrates at around 30% by weight of HCl. Any chlorine formed is absorbed in an alkaline aqueous solution. The fumes released into the atmosphere now contain only very low levels of free chlorine and other pollutants. 30% aqueous hydrochloric solutions can be sold as is for applications such as neutralization of alkaline effluents, preparations of metal chlorides, attack of metals, or can be treated to lead to more or less anhydrous hydrogen chloride. (HCI gas). The HCl gas can be used in particular for the manufacture of vinyl chloride obtained by thermal cracking of 1,2-dichloroethane, which is synthesized in particular by oxychlorination of ethylene, depending on the reaction:
C2H4 + 2HCIg + O2 - C2H4CI2 + H2O L' HCIg utilisé pour l' oxychloration de l'éthylène peut être obtenu à partir desdites solutions aqueuses chlorhydriques issues de VRC.C 2 H 4 + 2HCI g + O 2 - C 2 H 4 CI 2 + H 2 OL 'HCI g used for the oxychlorination of ethylene can be obtained from said aqueous hydrochloric solutions derived from HRV.
On opère selon le procédé décrit ci-après, schématisé sur la figure 1. La solution aqueuse chlorhydrique à 30 % provenant d'absorbeurs d'une unité VRC est dirigée vers une colonne de concentration (1) puis ensuite vers une colonne de distillation (2).The operation is carried out according to the process described below, shown diagrammatically in FIG. 1. The 30% hydrochloric aqueous solution coming from absorbers of an HRV unit is directed to a concentration column (1) then then to a distillation column ( 2).
Par chauffage au moyen du bouilleur (3) situé au pied de la colonne (2), un HCI gaz contenant quelques pour-cents d'eau (6 à 7 %) est vaporisé en (4). En pied de colonne (2), on obtient une solution aqueuse chlorhydrique à 21,5 % en poids d' HCI qui peut être recyclée à l'absorption VRC. Par refroidissements successifs de cet HCI gaz dans un premier condenseur à eau (5) puis dans des condenseurs à saumure (6) et (7) vers -12°C, on obtient un gaz HCI contenant de l'eau vapeur et de l'eau sous forme de vésicules qui sont éliminées dans un séparateur (8).By heating by means of the boiler (3) located at the foot of the column (2), an HCl gas containing a few percent of water (6 to 7%) is vaporized in (4). At the bottom of column (2), an aqueous hydrochloric solution containing 21.5% by weight of HCl is obtained which can be recycled for HRV absorption. By successive cooling of this HCI gas in a first water condenser (5) then in brine condensers (6) and (7) towards -12 ° C., an HCI gas is obtained containing steam water and water in the form of vesicles which are eliminated in a separator (8).
L' HCI gaz obtenu en (9) contient environ 50 à 150 pp d'eau. La demanderesse a constaté que l'utilisation d'un tel gaz pour l' oxychloration de l'éthylène entraînait des problèmes de corrosion importants des compresseurs utilisés pour amener HCI gaz à une pression (d'utilisation) d'environ 6 à 7 bars. Ces corrosions des compresseurs entraînent des abaissements des taux de compression conduisant à des arrêts fréquents pour remise en état. Il en résulte une maintenance élevée et coûteuse.The HCl gas obtained in (9) contains approximately 50 to 150 pp of water. The Applicant has found that the use of such a gas for the oxychlorination of ethylene leads to significant corrosion problems of the compressors used to bring HCl gas to a (operating) pressure of approximately 6 to 7 bars. These compressor corrosions lead to lower compression ratios leading to frequent shutdowns for reconditioning. This results in high and costly maintenance.
Par conséquent, il existe un réel besoin d'avoir un HCI gaz aussi anhydre que possible. Dans les appareillages mentionnés ci-dessus, il est nécessaire d'avoir un HCI gaz ayant une teneur en eau aussi faible que possible afin d'éviter toute condensation d'eau dans les conditions de température et de pression utilisées dans lesdits appareillages (compresseurs et conduites d' HCI).Therefore, there is a real need to have an HCI gas as anhydrous as possible. In the above-mentioned devices, it is necessary to have a gas HCI with a water content as low as possible in order to avoid any condensation of water under the temperature and pressure conditions used in said equipment (compressors and HMI pipes).
Cette teneur en eau dans HCI gaz peut être mesurée aisément par la détermination du point de rosée (ou température de liquéfaction commençante de l'eau acide) par abaissement de la température d'un échantillon d'HCI gaz à une pression donnée.This water content in HCI gas can be easily measured by determining the dew point (or starting liquefaction temperature of acidic water) by lowering the temperature of a sample of HCI gas at a given pressure.
De nombreuses techniques existent industriellement pour abaisser, voire éliminer l'eau de l'HCI gaz. A titre d'exemple, on citera le séchage sur zéolithes (WO 0020101) ; par passage sur un lit constitué de MgCI2 déposé sur différents supports tels que charbon actif (EP 1092678, EP 914863-Al), charbon micro poreux (EP 894527-Al) ; par mise en contact avec un chlorure de silicium (FR 2595958) ; au moyen de H3PO4, de H2SO4 (FR 2037540, GB 1057537, WO 0112541).Many techniques exist industrially to lower or even eliminate water from the HCI gas. By way of example, mention may be made of drying on zeolites (WO 0020101); by passing over a bed consisting of MgCl 2 deposited on various supports such as activated carbon (EP 1092678, EP 914863-Al), micro-porous carbon (EP 894527-Al); by contacting with a silicon chloride (FR 2595958); using H 3 PO 4 , H 2 SO 4 (FR 2037540, GB 1057537, WO 0112541).
Parmi toutes ces techniques, on citera tout particulièrement celles qui utilisent H2SO , et notamment celle décrite dans la demande internationale WO 0112541.Among all these techniques, particular mention will be made of those which use H 2 SO, and in particular that described in international application WO 0112541.
Le procédé décrit dans cette demande consiste à traiter un HCI gaz provenant d'une unité d' incinération de résidus chlorés et qui contient encore une teneur en eau résiduelle trop importante qui est de nature à entraîner la corrosion de compresseurs et de conduites utilisées pour véhiculer ledit HCI. La figure 2 représente d'une façon schématique le procédé de séchage décrit dans WO 0112541 utilisant H25O4 qui permet de parfaire le séchage d'un HCI gaz et d'amener sa teneur en eau inférieure à 0,5 ppm voire inférieur à 0,15 ppm.The process described in this application consists in treating an HCl gas originating from a chlorinated residue incineration unit and which still contains an excessively high residual water content which is liable to cause corrosion of the compressors and pipes used to convey said HCI. FIG. 2 schematically represents the drying method described in WO 0112541 using H 2 5O 4 which makes it possible to perfect the drying of an HCl gas and to bring its water content less than 0.5 ppm or even less than 0.15 ppm.
Pour ce faire, l'auteur de la demande WO 0112541 met en oeuvre un procédé de séchage compliqué et coûteux utilisant des colonnes à garnissage, (92), (96), un compresseur à anneau liquide (88) des stockages d'H2SO4 (114), (84) et toute une installation de recyclage de I ' H2SO4. .To do this, the author of the application WO 0112541 implements a complicated and costly drying process using packed columns, (92), (96), a liquid ring compressor (88) for H 2 storage. SO 4 (114), (84) and a whole installation for recycling H 2 SO 4 . .
L' HCI gaz à traiter arrive en (81) dans une colonne à garnissage (92). L'H2SO sec est prélevé d'un Stockage (82) puis amené à une cuve ventilée (84). Ensuite, H25O4 sec (86) est pompé vers un compresseur à anneau liquide (88) ou il est mis en contact avec HCI gaz partiellement sec (90) provenant de la tête d'une première colonne d'absorption à garnissage (92), lequel reçoit HCI gaz à sécher (81) et avec un courant (94) dΗ2SO partiellement humide recyclé provenant d'une seconde colonne d'absorption à garnissage (96). L' HCI partiellement séché (90) provenant de (92) est ensuite séché dans (96) pour fournir HCI anhydre (98). L' H2S04 partiellement humide en bas de (96) recyclée en partie à ladite colonne, alimente le compresseur (88) via (100) et la colonne (92) via (102) où il est mis en contact à contre courant avec le courant d'HCI gaz à sécher (81).The HCl gas to be treated arrives at (81) in a packed column (92). The dry H 2 SO is taken from a storage (82) and then brought to a ventilated tank (84). Then, H 2 5O 4 sec (86) is pumped to a liquid ring compressor (88) or it is brought into contact with HCl partially dry gas (90) coming from the head of a first packed absorption column ( 92), which receives HCI gas to be dried (81) and with a stream (94) dΗ 2 SO partially wet recycled from a second packed absorption column (96). The partially dried HCI (90) from (92) is then dried in (96) to provide anhydrous HCI (98). The partially wet H 2 S0 4 at the bottom of (96) partially recycled to said column, feeds the compressor (88) via (100) and the column (92) via (102) where it is brought into contact against the current. with the HCl gas stream to be dried (81).
L' H2504 humide obtenu en pied de (92) est recyclé en partie au sommet de ladite colonne (92) et en partie dans une colonne de stripping (106) qui utilise de l'air sec (108) pour éliminer HCI résiduel de H2SO humide, lequel HCI est éliminé en tête (110). L' H2SO humide, débarrassé de HCI est récupéré dans un bac de stockage (114) où il est ultérieurement séché pour être réutilisé.The wet H 2 50 4 obtained at the bottom of (92) is recycled partly at the top of said column (92) and partly in a stripping column (106) which uses dry air (108) to remove HCI residual wet H 2 SO, which HCI is eliminated at the top (110). The wet H 2 SO, free of HCI, is recovered in a storage tank (114) where it is subsequently dried for reuse.
Bien que ce procédé permet d'obtenir un HCI gaz anhydre, il présente (comme tous les procédés utilisant H2SO ) l'inconvénient de pouvoir générer des ions sulfates.Although this process makes it possible to obtain an anhydrous HCl gas, it has (like all the processes using H 2 SO) the disadvantage of being able to generate sulphate ions.
En outre, ce procédé nécessite un investissement en matériel important et coûteux (colonnes, cuves de stockage, compresseur...) et génère de l'acide sulfurique humide dilué dont la valorisation nécessite soit un séchage soit une purification.In addition, this process requires an investment in large and expensive equipment (columns, storage tanks, compressor ...) and generates dilute wet sulfuric acid whose recovery requires either drying or purification.
La demanderesse a maintenant trouvé que l'on pouvait obtenir un HCI gaz anhydre plus simplement, obtenu lors de la distillation de solutions aqueuses chlorhydriques provenant notamment de VRC, en évitant les inconvénients mentionnés précédemment en utilisant, dans certaines conditions, du CaCI2 anhydre.The Applicants have now found that an anhydrous HCl gas can be obtained more simply, obtained during the distillation of aqueous hydrochloric solutions originating in particular from HRV, by avoiding the drawbacks mentioned previously by using, under certain conditions, anhydrous CaCl 2 .
L' invention a donc pour objet un procédé de séchage de chlorure d'hydrogène provenant de la distillation de solutions aqueuses chlorhydriques obtenues notamment lors de la valorisation de résidus chlorés, caractérisé en ce que ledit chlorure d'hydrogène est mis en contact avec du chlorure de calcium anhydre (CaC\z) pendant une durée inférieure ou égale à 1 minute et, de préférence, comprise entre 5 secondes et 45 secondes.The subject of the invention is therefore a process for drying hydrogen chloride originating from the distillation of aqueous hydrochloric solutions obtained in particular during the recovery of chlorinated residues, characterized in that said hydrogen chloride is brought into contact with chloride anhydrous calcium (CaC \ z) for a period of time less than or equal to 1 minute and, preferably, between 5 seconds and 45 seconds.
Selon la présente invention, l' HCI gaz provient d'une installation de valorisation de résidus chlorés (VRC) telle que décrite précédemment et présente une teneur en eau généralement comprise entre 150 et 200 ppm. Le CaCI2 anhydre, utilisable selon la présente invention se trouve être sous forme de perles de diamètre inférieur ou égal à 5 mm et, de préférence, de diamètre allant de 1 à 5 mm.According to the present invention, the HCI gas comes from a chlorinated residue recovery plant (HRV) as described above and has a water content generally between 150 and 200 ppm. The anhydrous CaCl 2 which can be used according to the present invention is found to be in the form of beads with a diameter less than or equal to 5 mm and, preferably, with a diameter ranging from 1 to 5 mm.
Le séchage du chlorure d'hydrogène s'effectue à une température allant de -30°C à 20°C et, de préférence, allant de -15°C à -10°C. Il s'effectue généralement à une pression égale ou supérieure à la pression atmosphérique, et de préférence, à la pression de distillation fournissant l'HCI gaz humide à sécher. Le temps de séjour ou temps de contact de l' HCI gaz avec le CaCI2 anhydre doit être suffisant pour absorber l'eau résiduelle. Il est fonction de la charge utilisée et du débit de gaz HCI humide à sécher.The drying of the hydrogen chloride is carried out at a temperature ranging from -30 ° C to 20 ° C and, preferably, ranging from -15 ° C to -10 ° C. It is generally carried out at a pressure equal to or greater than atmospheric pressure, and preferably at the distillation pressure supplying the HCl humid gas to be dried. The residence time or contact time of the gas HCI with the CaCI 2 anhydrous must be sufficient to absorb the residual water. It depends on the load used and the flow rate of humid HCI gas to be dried.
Avantageusement, ce temps est égal ou inférieur à 1 min, généralement, ce temps de séjour va de 5 sec à 45 sec. L'homme du métier déterminera la charge de CaCI2 anhydre ainsi que le débit d'HCI gaz pour tomber dans les temps de séjour préalablement mentionnés.Advantageously, this time is equal to or less than 1 min, generally, this residence time ranges from 5 sec to 45 sec. Those skilled in the art will determine the charge of anhydrous CaCl 2 as well as the flow of HCI gas to fall within the residence times previously mentioned.
La durée de vie du CaCI2 anhydre utilisée peut être calculée en tenant compte de la masse d'eau absorbée par masse de CaCI2 anhydre mis en œuvre.The lifetime of the anhydrous CaCI 2 used can be calculated by taking into account the mass of water absorbed per mass of anhydrous CaCI 2 used.
La demanderesse a constaté qu' il est nécessaire de changer la charge de CaCI2 lorsque celle-ci a augmenté de 30 % en poids au plus et, de préférence, lorsque la charge a augmenté de 25 à 30 %.The Applicant has found that it is necessary to change the load of CaCI 2 when the latter has increased by 30% by weight at most and, preferably, when the load has increased by 25 to 30%.
Cet optimum ne doit pas être dépassé sous peine d'aboutir à un séchage inefficace et d'avoir une charge plus ou moins déliquescente, qui serait difficile à éliminer et, qui plus est, pourrait entraîner des surpressions dues au colmatage des grains de Ca l2.This optimum must not be exceeded under penalty of leading to ineffective drying and of having a more or less deliquescent load, which would be difficult to remove and, moreover, could lead to overpressures due to clogging of the grains of Ca l 2 .
La teneur en eau dans l' HCI gaz ayant traversé la charge de CaCI2 peut être aisément obtenue par la détermination du point de rosée de HCI gaz sortant.The water content in the HCl gas having passed through the CaCI 2 feed can be easily obtained by determining the dew point of the outgoing HCl gas.
Le procédé selon la présente invention peut être mis en oeuvre au moyen d'un dispositif tel que représenté schématiquement sur la figure 3.The method according to the present invention can be implemented by means of a device as shown diagrammatically in FIG. 3.
Ce dispositif est caractérisé en ce qu'il comprend :This device is characterized in that it comprises:
- une colonne cylindrique verticale (01) comprenant au moins un panier (02) contenant la charge de CaCI2 anhydre, ayant à sa base une grille de fond (03) munie de lamelles entrecroisées et une grille support (04) sur laquelle repose une toile (05) ; à la partie supérieure dudit panier repose également sur la charge de CaCl2 une toile (06) ;- a vertical cylindrical column (01) comprising at least one basket (02) containing the charge of anhydrous CaCl 2 , having at its base a bottom grid (03) provided with interlaced strips and a support grid (04) on which a canvas (05); at the upper part of said basket also rests on the load of CaCl 2 a fabric (06);
- un fond cylindrosphérique (07) muni d'une arrivée de gaz HCI (08) en jonction avec un "sabre" d'injection (09) muni de trous disposés en quinconce (non représenté sur la figure 3), et d'une purge (10) ; - un chapeau cylindrosphérique (11) muni d'une sortie d' HCI sec (12) et d'oreilles de levage (13).a cylindrical bottom (07) provided with an HCI gas inlet (08) in junction with an injection "saber" (09) provided with staggered holes (not shown in FIG. 3), and a purge (10); - a cylindrical cap (11) provided with a dry HCI outlet (12) and lifting lugs (13).
Les toiles (04) et (05) sont constituées en un matériau résistant à l'HCI et possèdent des mailles de diamètre égal à environ 1 mm.The fabrics (04) and (05) are made of a material resistant to HCl and have meshes of diameter equal to approximately 1 mm.
Selon la présente invention, la charge de CaC\z est aisément remplacée du fait de la simplicité du dispositif utilisé. Ce remplacement consiste à déposer le chapeau (11), à enlever le panier contenant la charge usagée et à remettre un nouveau panier contenant une charge neuve de CaCI2. Cette façon d'opérer permet d'avoir une durée d' intervention très courte. La colonne cylindrique (01), le fond (06), le chapeau (10), ainsi que la sabre d' injection (08) et les grilles (03) et (04) sont en matériaux résistant à la corrosion tels que acier ébonité, polypropylène enrubanné d'un matériau composite. Le (ou les) panier(s) est (sont) en polypropylène haute densitéAccording to the present invention, the charge of CaC \ z is easily replaced due to the simplicity of the device used. This replacement consists of removing the cap (11), removing the basket containing the used charge and replacing a new basket containing a new charge of CaCI 2 . This way of operating allows for a very short intervention time. The cylindrical column (01), the bottom (06), the cap (10), as well as the injection saber (08) and the grids (03) and (04) are made of corrosion resistant materials such as ebonity steel. , polypropylene wrapped in a composite material. The basket (s) is (are) made of high density polypropylene
(PPHD).(PPHD).
Le procédé conforme à l' invention présente une grande souplesse, a l'avantage d'utiliser un dispositif simple et peu coûteux pouvant s' intercaler facilement dans des unités existantes et conduit à un HCI gaz ayant des teneurs en eau inférieures à 20 ppm voire inférieures à 10 ppm.The process according to the invention has great flexibility, has the advantage of using a simple and inexpensive device which can be easily inserted into existing units and results in an HCl gas having water contents of less than 20 ppm or even less than 10 ppm.
L'exemple qui suit illustre l' invention. a) L'appareillage utilisé est tel que représenté sur la figure (3), excepté que l'on utilise 2 paniers (02), présente les caractéristiques suivantes :The following example illustrates the invention. a) The apparatus used is as shown in Figure (3), except that 2 baskets (02) are used, has the following characteristics:
- dimensions de la colonne (01) : - hauteur : 6,203 m,- dimensions of the column (01): - height: 6.203 m,
- diamètre intérieur : 1 m ;- inside diameter: 1 m;
- dimensions du fond (07) :- bottom dimensions (07):
- hauteur : 0,75 m,- height: 0.75 m,
- diamètre intérieur : 1 m, - sabre d' injection (09) constitué d'un tube de longueur totale égale à- internal diameter: 1 m, - injection saber (09) consisting of a tube of total length equal to
1,293 m et de diamètre égal à 0,20 m percé sur une longueur de 0,84 m de 9 rangées de 11 trous de diamètre égal à 12 mm disposés en quinconce ;1,293 m and diameter equal to 0.20 m drilled over a length of 0.84 m from 9 rows of 11 holes of diameter equal to 12 mm arranged in staggered rows;
- dimensions du chapeau (11) : - hauteur : 0,75 m,- hat dimensions (11): - height: 0.75 m,
- diamètre intérieur : 1 m ;- inside diameter: 1 m;
- dimensions des paniers (02) - les 2 paniers sont identiques :- dimensions of the baskets (02) - the 2 baskets are identical:
- hauteur totale : 3,10 m contenant la charge de CaC\z sur une hauteur de 2,90 m, - diamètre intérieur : 0,93 m ;- total height: 3.10 m containing the charge of CaC \ z over a height of 2.90 m, - internal diameter: 0.93 m;
- les grilles de fond (03) ont un diamètre extérieur de 0,905 m et les grilles support (04) ont un diamètre extérieur de 0,91 m ;- the bottom grids (03) have an outside diameter of 0.905 m and the support grids (04) have an outside diameter of 0.91 m;
- les toiles (04) et (05) ont des mailles de diamètre égaux à 1 mm et sont en PPHD. La colonne est en polypropylène haute densité, enrubanné par un stratifié verre polyester. b) Conditions opératoires : T FR03/00307- the fabrics (04) and (05) have meshes of diameter equal to 1 mm and are made of PPHD. The column is made of high density polypropylene, wrapped in a polyester glass laminate. b) Operating conditions: T FR03 / 00307
77
Chaque panier est chargé avec 1,3 tonne de CaC\z anhydre qui se présente sous forme de perles de 1 à 5 mm de diamètre.Each basket is loaded with 1.3 tonnes of anhydrous CaC \ z which is in the form of beads from 1 to 5 mm in diameter.
L' HCI gaz à sécher provient de la distillation de solutions chlorhydriques d'une unité VRC telle que décrite précédemment et schématisée sur la figure 1 (sortie (7)).The HCl gas to be dried comes from the distillation of hydrochloric solutions from an HRV unit as described above and shown diagrammatically in Figure 1 (outlet (7)).
Cet HCI gaz a une teneur moyenne en eau égale à 200 ppm et est introduit en (08) à un débit variant entre 0,5 et 2,5 t/h à une température de -13°C.This HCl gas has an average water content equal to 200 ppm and is introduced in (08) at a flow rate varying between 0.5 and 2.5 t / h at a temperature of -13 ° C.
La pression dans le dispositif est de 0,8 bar relatif. On détermine périodiquement par la méthode du point de rosée la teneur en eau dans HCI sortant en (12) et l'on trouve un point de rosée de -24°C (mesuré sous pression atmosphérique), ce qui correspond à une teneur en eau d'environ 15 ppm. The pressure in the device is 0.8 bar relative. The water content in HCI leaving at (12) is determined periodically by the dew point method and a dew point of -24 ° C. is found (measured at atmospheric pressure), which corresponds to a water content about 15 ppm.

Claims

REVENDICATIONS
* * * * * * ** * * * * * *
Procédé de séchage de chlorure d'hydrogène provenant de solutions aqueuses chlorhydriques, caractérisé en ce que ledit chlorure d'hydrogène est mis en contact avec du chlorure de calcium anhydre (CaCI2) pendant une durée inférieure ou égale à 1 minute.Method for drying hydrogen chloride from aqueous hydrochloric solutions, characterized in that said hydrogen chloride is brought into contact with anhydrous calcium chloride (CaCl 2 ) for a period of time less than or equal to 1 minute.
Procédé selon la revendication 1, caractérisé en ce que le chlorure d' hydrogène est mis en contact avec du CaCI2 anhydre pendant une durée comprise entre 5 secondes et 45 secondes.Process according to claim 1, characterized in that the hydrogen chloride is brought into contact with anhydrous CaCl 2 for a period of between 5 seconds and 45 seconds.
Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que le chlorure de calcium anhydre (CaCI2) est sous forme de perles de diamètre inférieur ou égal à 5 mm et, de préférence, de diamètre allant de 1 à 5 mm.Method according to one of claims 1 or 2, characterized in that the anhydrous calcium chloride (CaCl 2 ) is in the form of beads with a diameter less than or equal to 5 mm and, preferably, with a diameter ranging from 1 to 5 mm .
Procédé selon l'une des revendications 1 à 3, caractérisé en ce que le séchage s'effectue à une température allant de -30°C à 20°C.Method according to one of claims 1 to 3, characterized in that the drying takes place at a temperature ranging from -30 ° C to 20 ° C.
Procédé selon la revendication 4, caractérisé en ce que le séchage s'effectue à une température allant de -15°C à -10°C.Process according to Claim 4, characterized in that the drying takes place at a temperature ranging from -15 ° C to -10 ° C.
Procédé selon l'une des revendications 1 à 4, caractérisé en ce que le séchage s'effectue sous une pression égale ou supérieure à la pression atmosphérique.Method according to one of claims 1 to 4, characterized in that the drying is carried out under a pressure equal to or greater than atmospheric pressure.
Application du procédé selon l'une des revendications 1 à 6 au séchage de chlorure d'hydrogène provenant de solutions aqueuses chlorhydriques obtenues lors de la valorisation des résidus chlorésApplication of the method according to one of claims 1 to 6 to the drying of hydrogen chloride from aqueous hydrochloric solutions obtained during the recovery of chlorinated residues
(VRC).(HRV).
Dispositif pour mettre en oeuvre le procédé selon l'une des revendications 1 à 7, caractérisé en ce qu' il comprend : - une colonne cylindrique verticale (01) comprenant au moins un panierDevice for implementing the method according to one of Claims 1 to 7, characterized in that it comprises: - a vertical cylindrical column (01) comprising at least one basket
(02) contenant la charge de CaCI2 anhydre, ayant à sa base une grille de fond (03) munie de lamelles entrecroisées et une grille support (04) sur laquelle repose une toile (05) ; à la partie supérieure dudit panier repose également sur la charge de CaCI2 une toile (06) ;(02) containing the charge of anhydrous CaCl 2 , having at its base a bottom grid (03) provided with interlaced lamellae and a support grid (04) on which a canvas (05) rests; at the upper part of said basket also rests on the load of CaCI 2 a canvas (06);
- un fond cylindrosphérique (07) muni d'une arrive de gaz HCI (08) en jonction avec un "sabre" d' injection (09) muni de trous disposés en quinconce (non représenté sur la figure 3), et d'une purge (10) ;- A cylindrical bottom (07) provided with an HCI gas inlet (08) in junction with an injection "saber" (09) provided with staggered holes (not shown in FIG. 3), and a purge (10);
- un chapeau cylindrosphérique (11) muni d'une sortie d' HCI sec (12) et d'oreilles de levage (13). - a cylindrical cap (11) provided with a dry HCI outlet (12) and lifting lugs (13).
EP03717366A 2002-02-18 2003-01-31 Method for drying of hydrogen chloride from aqueous hydrogen chloride solutions Withdrawn EP1480908A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0202011 2002-02-18
FR0202011A FR2836139B1 (en) 2002-02-18 2002-02-18 PROCESS FOR DRYING HYDROGEN FENCE FROM AQUEOUS HYDROCHLORIC SOLUTIONS
PCT/FR2003/000307 WO2003070630A1 (en) 2002-02-18 2003-01-31 Method for drying hydrogen chloride from hydrochloric aqueous solutions

Publications (1)

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EP1480908A1 true EP1480908A1 (en) 2004-12-01

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ID=27636261

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AU (1) AU2003222351A1 (en)
FR (1) FR2836139B1 (en)
WO (1) WO2003070630A1 (en)

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US10477883B2 (en) 2015-08-25 2019-11-19 Cornelius, Inc. Gas injection assemblies for batch beverages having spargers
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FR2836139B1 (en) 2004-10-22
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AU2003222351A1 (en) 2003-09-09

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